ABSTRACT
Chiral aggregation structure spontaneously formed by achiral rodlike molecules, a long-time unsolved problem in liquid crystal science, has been clarified by applying a new crystallographic algorithm recently developed while utilizing aggregation characteristics of this type. Bicontinuously interwoven networks characterize it similarly to the neighboring Gyroid phase in a phase diagram against the alkyl chain length and temperature. However, the network connectivity is significantly different from the bicontinuous networks that have been either known for related compounds or assumed for this phase. The network is compatible with the homochiral arrangement of rodlike molecules with successive twists by a proper angle between adjacent junctions.
ABSTRACT
Recently, two molecular packing modes of the alkyl chain in smectic A (SmA) liquid crystal phases were revealed: normal and tilted types, which are named by the orientation relative to the layer normal. This study reveals the relationship between the packing mode and thermodynamic order of the SmA-nematic (N) phase transition. Two normal type and three tilted type mesogens were subject to thermodynamic and structural experiments. The DSC results showed that the SmA-N phase transitions of the normal and tilted types are of the second and first order, respectively. The analysis of the intensities of reflections in wide-angle X-ray diffraction related to the periodicity of the SmA layer yielded the distribution of the mass centers of molecules along the normal to the SmA layers. The resultant distribution offered a rationale for the correlation of the thermodynamic order of the SmA-N phase transition and molecular packing modes in the SmA phases based on the Meyer-Lubensky theory.
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Two types of binary mixtures were examined to optimize the siloxanyl fraction by filling the gap between the two Cub-phase-forming molecules with di- and tri-siloxanyl terminals. Adding siloxanyl to the disiloxanyl system largely inhibited crystallization, increasing the stability at room temperature of the meta-stable Ia3Ìd phase obtained by cooling from the high-temperature phase. The effect was prominent for the mixtures containing both di- and tri-siloxanyl compounds. The most prominent result was obtained for the 50 : 50 mixture; the Ia3Ìd phase was quite stable and survived at room temperature after more than 1 year, as if it were like a thermodynamically stable phase.
ABSTRACT
Technologies to fold structures into compact shapes are required in multiple engineering applications. Earwigs (Dermaptera) fold their fanlike hind wings in a unique, highly sophisticated manner, granting them the most compact wing storage among all insects. The structural and material composition, in-flight reinforcement mechanisms, and bistable property of earwig wings have been previously studied. However, the geometrical rules required to reproduce their complex crease patterns have remained uncertain. Here we show the method to design an earwig-inspired fan by considering the flat foldability in the origami model, as informed by X-ray microcomputed tomography imaging. As our dedicated designing software shows, the earwig fan can be customized into artificial deployable structures of different sizes and configurations for use in architecture, aerospace, mechanical engineering, and daily use items. Moreover, the proposed method is able to reconstruct the wing-folding mechanism of an ancient earwig relative, the 280-million-year-old Protelytron permianum This allows us to propose evolutionary patterns that explain how extant earwigs acquired their wing-folding mechanism and to project hypothetical, extinct transitional forms. Our findings can be used as the basic design guidelines in biomimetic research for harnessing the excellent engineering properties of earwig wings, and demonstrate how a geometrical designing method can reveal morphofunctional evolutionary constraints and predict plausible biological disparity in deep time.
ABSTRACT
N-C axially chiral 3-(2-trideuteriomethyl-4,6-dimethylphenyl)-2-ethylquinazolin-4-ones and 3-(2-trideuteriomethyl-4,6-dimethylphenyl)-2-(1-phenylpropan-2-yl)quinazolin-4-ones were prepared in high enantio- and diastereomeric purities (98% ee). These quinazolinone derivatives are isotopic atropisomers based on ortho-CH3/CD3 discrimination and were revealed to possess a slight optical rotation and high rotational stability.
Subject(s)
StereoisomerismABSTRACT
This paper characterizes the molecular mobility that triggers the cold crystallization abilities in 5'-(2,3-difluorophenyl)-2'-ethoxy-4-pentyloxy-2,3-difluorotolane (short name DFP25DFT) material by broadband dielectric spectroscopy (BDS). We analyze the properties of identified molecular motions by referring to the Vogel-Fulcher-Tammann (VFT) model for the structural α-process associated with molecular rotation in isotropic liquid and the Eyring and Starkweather approach for the thermally activated processes, ß-process related to intramolecular movement in liquid and glassy state and emerging during cold crystallization α'-process ascribed to confined movements of molecules located adjacent to crystalline surfaces. To characterize the material, we employ single-crystal X-ray diffraction, differential scanning calorimetry (DSC), adiabatic calorimetry, and polarizing optical microscopy (POM), while we utilize molecular mechanics simulations (MM2) to explore molecular flexibility. Our study focuses on inter- and intramolecular interactions that determine the cold-crystallization tendency. We demonstrate that the solidification path is controlled by the fragility of the system, the dipole-dipole attraction, and the intramolecular dynamics. The study of cold crystallization kinetics under isothermal conditions reveals the complexity of the process: the formation of two crystalline phases, Cr2 and Cr3, proceeding in different modes. This feature discloses the possibility of switching the crystal growth between three- and two-dimensional in the cold-crystallization process driven by different mechanisms.
Subject(s)
Glass , Molecular Dynamics Simulation , Crystallization , Kinetics , Calorimetry, Differential Scanning , Glass/chemistryABSTRACT
BACKGROUND AND AIMS: Frailty and sarcopenia are common and confer poor prognosis in elderly patients with heart failure; however, gender differences in its prevalence or prognostic impact remain unclear. METHODS AND RESULTS: We included 1332 patients aged ≥65 years, who were hospitalized for heart failure. Frailty and sarcopenia were defined using the Fried phenotype model and Asian Working Group for Sarcopenia criteria, respectively. Gender differences in frailty and sarcopenia, and interactions between sex and prognostic impact of frailty/sarcopenia on 1-year mortality were evaluated. Overall, 53.9% men and 61.0% women and 23.7% men and 14.0% women had frailty and sarcopenia, respectively. Although sarcopenia was more prevalent in men, no gender differences existed in frailty after adjusting for age. On Kaplan-Meier analysis, frailty and sarcopenia were significantly associated with 1-year mortality in both sexes. On Cox proportional hazard analysis, frailty was associated with 1-year mortality only in men, after adjusting for confounding factors (hazard ratio [HR], 1.94; 95% confidence interval [CI], 1.19-3.16; P = 0.008 for men; HR, 1.63; 95% CI, 0.84-3.13; P = 0.147 for women); sarcopenia was an independent prognostic factor in both sexes (HR, 1.93; 95% CI, 1.13-3.31; P = 0.017 for men; HR, 3.18; 95% CI, 1.59-5.64; P = 0.001 for women). There were no interactions between sex and prognostic impact of frailty/sarcopenia (P = 0.806 for frailty; P = 0.254 for sarcopenia). CONCLUSIONS: Frailty and sarcopenia negatively affect older patients with heart failure from both sexes. CLINICAL TRIALS: This study was registered at the University Hospital Information Network (UMIN-CTR, unique identifier: UMIN000023929) before the first patient was enrolled.
Subject(s)
Frailty , Heart Failure , Sarcopenia , Aged , Female , Frail Elderly , Frailty/diagnosis , Frailty/epidemiology , Heart Failure/complications , Heart Failure/diagnosis , Heart Failure/epidemiology , Humans , Male , Prevalence , Prognosis , Sarcopenia/complications , Sarcopenia/diagnosis , Sarcopenia/epidemiology , Sex Characteristics , Sex FactorsABSTRACT
BACKGROUND: The purpose of this study was to clarify the prevalence, association with frailty and exercise capacity, and prognostic implication of sarcopenic obesity in patients with heart failure. METHODS: The present study included 779 older adults hospitalized with heart failure (median age: 81 years; 57.4% men). Sarcopenia was diagnosed based on the guidelines by the Asian Working Group for Sarcopenia. Obesity was defined as the percentage of body fat mass (FM) obtained by bioelectrical impedance analysis. The FM cut-off points for obesity were 38% for women and 27% for men. The primary endpoint was 1-year all-cause death. We assessed the associations of sarcopenic obesity occurrence with the short physical performance battery (SPPB) score and 6-minute walk distance (6MWD). RESULTS: The rates of sarcopenia and obesity were 19.3 and 26.2%, respectively. The patients were classified into the following groups: non-sarcopenia/non-obesity (58.5%), non-sarcopenia/obesity (22.2%), sarcopenia/non-obesity (15.3%), and sarcopenia/obesity (4.0%). The sarcopenia/obesity group had a lower SPPB score and shorter 6MWD, which was independent of age and sex (coefficient, - 0.120; t-value, - 3.74; P < 0.001 and coefficient, - 77.42; t-value, - 3.61; P < 0.001; respectively). Ninety-six patients died during the 1-year follow-up period. In a Cox proportional hazard analysis, sarcopenia and obesity together were an independent prognostic factor even after adjusting for a coexisting prognostic factor (non-sarcopenia/non-obesity vs. sarcopenia/obesity: hazard ratio, 2.48; 95% confidence interval, 1.22-5.04; P = 0.012). CONCLUSION: Sarcopenic obesity is a risk factor for all-cause death and low physical function in older adults with heart failure. TRIAL REGISTRATION: University Hospital Information Network (UMIN-CTR: UMIN000023929 ).
Subject(s)
Heart Failure , Sarcopenia , Aged , Aged, 80 and over , Female , Heart Failure/complications , Heart Failure/diagnosis , Heart Failure/epidemiology , Humans , Male , Obesity/complications , Obesity/diagnosis , Obesity/epidemiology , Prevalence , Risk Factors , Sarcopenia/diagnosis , Sarcopenia/epidemiologyABSTRACT
Multicore photonic crystal fiber (MC-PCF) can scale the output power with the number of cores by spatial beam combining if the in-phase mode is selected. We demonstrated simultaneous realization of phase-locked and mode-locked laser using Yb-doped 7-core MC-PCF by a semiconductor saturable absorber placed in the near-field inside a resonator. High energy 333 nJ pulses were obtained directly from a mode-locked fiber laser oscillator at a 42.4 MHz repetition rate with an average power of 14.1 W at 24 W excitation. We observed the direct output pulse width of 52 ps assuming a sech2 profile. However, it might be noise-like pulses because of no variation when we performed pulse compression. Single-pulse operation was achieved by increasing the bandwidth of the intracavity filter. In this case, 137 nJ, 42.4 MHz pulses were generated with a 5.8 W average power and the compressed output pulse width was 8.6 ps.
ABSTRACT
A recent intriguing finding that a helical network arrangement forms the bicontinuous cubic phase is attracting great attention for the possibility of new routes to asymmetric synthesis by achiral molecules. However, the design of the molecular structure for the cubic phase is still unrevealed. In this work, a nonsymmetric core molecule with larger naphthalene and smaller benzene moieties at each side of the central linkage and the same disiloxanyldecyloxy terminal at both terminals is shown to be the first example of molecule forming both single-layered and double-layered core assembly modes in the Ia3d phase as a single molecule system. The molecule forms the former mode at high temperatures as a thermodynamically stable phase, similarly to the symmetric naphthalene core system, whereas, on cooling below a temperature (â¼350â K), a metastable Ia3d phase forms a double-layered core state down to room temperature, which is common to the benzene core system. As another effect of the nonsymmetric core, the cubic phase is maintained at room temperature for more than 100â days with slight distortion. Infrared spectral studies and quantum chemical calculations suggested the easy transformation between the two core assembly modes. The core nonsymmetry can be a versatile fine-tuning of the core assembly mode and phase stability for the cubic phase molecules.
ABSTRACT
Control over the stacking patterns in 2D molecular assemblies is demonstrated using chemical modification. A target system is a hydrogen-bonded cocrystal (2:1) composed of 2-pyrrolidone (Py) and chloranilic acid (CA) (PyCA). X-ray crystallography showed that weak intersheet interactions give rise to a variety of metastable overlapping patterns comprised of the 2D assemblies mainly formed via hydrogen bonds, affording reversible and irreversible structural phase transitions. We prepared cocrystals of Py and anilic acids bearing different halogens, in which 2D assemblies isostructural with those observed in PyCA exhibit various overlapping patterns. The order of stability for each overlapping pattern estimated using calculations of the intermolecular interactions did not completely coincide with those indicated by our experimental results, which can be explained by considering the entropic effect: the molecular motion of Py as detected using nuclear quadrupole resonance spectroscopy.
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We report that user-defined DNA nanostructures, such as two-dimensional (2D) origamis and nanogrids, undergo a rapid higher-order folding transition, referred to as supra-folding, into three-dimensional (3D) compact structures (origamis) or well-defined µm-long ribbons (nanogrids), when they adsorb on a soft cationic substrate prepared by layer-by-layer deposition of polyelectrolytes. Once supra-folded, origamis can be switched back on the surface into their 2D original shape through addition of heparin, a highly charged anionic polyelectrolyte known as an efficient competitor of DNA-polyelectrolyte complexation. Orthogonal to DNA base-pairing principles, this reversible structural reconfiguration is also versatile; we show in particular that 1)â it is compatible with various origami shapes, 2)â it perfectly preserves fine structural details as well as site-specific functionality, and 3)â it can be applied to dynamically address the spatial distribution of origami-tethered proteins.
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Although the transition between a bilayer and an interdigitated membrane of a surfactant and lipid has been widely known for long, its mechanism remains unclear. This study reveals the transition mechanism of a cationic surfactant, dioctadecyldimethylammonium chloride (DODAC), through experiments and theoretical calculations. Experimentally, the transition from the interdigitated to bilayer structure in the gel phase of DODAC is found to be induced by adding hydrophobic molecules such as n-alkane and its derivatives. Further addition induces a different transition to another bilayer phase. Our theory, considering the competition of the electrostatic interaction between cationic headgroups and the hydrophobic interaction emerging at the alkyl-chain ends exposed to water, reproduces these two phase transitions. In addition, changes in alkyl-chain packing in the membranes at these transitions are reproduced. The underlying mechanism is that the interdigitated membrane is formed at a small additive content due to electrostatic repulsion. As the energetic disadvantage with respect to the hydrophobic interaction becomes dominant as the content increases, the transition to the bilayer occurs at a specific content. The bilayer-bilayer transition at a higher content is induced by the change in the balance of these interactions. Based on a similar concept, we suggest the mechanism of the additive-induced bilayer-interdigitated transition of phospholipids, i.e., neutrally charged (zwitterionic) surfactants.
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This article presents the molecular dynamics and solidification behavior of a 2,3-difluoro-4-propylphenyl 2,3-difluoro-4-(4-pentylcyclohexyl)benzoate nematic liquid crystal (5C4FPB3) observed by broadband dielectric spectroscopy (BDS) and differential scanning calorimetry (DSC). Polarized optical microscopy (POM) is also performed to confirm the phase transition temperatures. Our investigation reveals rare crystallization of the orientationally disordered crystal (ODIC) phase from the nematic phase and a glass transition of the crystal at cooling rates higher than 1 K min-1. The deconvolution of the dielectric spectra with derivative techniques is necessary because of the complex molecular dynamics in the crystalline phase. The BDS method enables us to capture the relaxation processes reflecting pre-crystallization molecular movements. The kinetics of nonisothermal crystallization is studied using the Ozawa, Mo, and isoconversional methods. The present studies suggest that the dominant factor of the crystal growth mechanism depends on the cooling rate. Two types of crystallization mechanisms are identified at cooling rates lower and higher than 5 K min-1. We design a diagram with crystallization and glass transition borders against the cooling rates. Estimations show that crystallization of the present compound can be bypassed at cooling rates higher than 78 kK min-1, at which a glass transition of the nematic phase occurs. We show various scenarios of the molecular order and the crystallization mechanism designed based on the process rate.
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The relationship between the membrane bending modulus (κ) and compressibility modulus (KA) depends on the extent of coupling between the two monolayers (leaflets). Using neutron spin echo (NSE) spectroscopy, we investigate the effects of n-alkanes on the interleaflet coupling of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) bilayers. Structural studies with small-angle X-ray and neutron scattering (SAXS and SANS) showed that the bilayer thickness increased with increasing n-alkane length, while NSE suggested that the bilayers became softer. Additional measurements of the membrane thickness fluctuations with NSE suggested that the changes in elastic moduli were due to a decrease in coupling between the leaflets upon addition of the longer n-alkanes. The decreased coupling with elongating n-alkane length was explained based on the n-alkane distribution within the bilayers characterized by SANS measurement of bilayers composed of protiated DPPC and deuterated n-alkanes. A higher fraction of the incorporated long n-alkanes were concentrated at the central plane of the bilayers and decreased the physical interaction between the leaflets. Using NSE and SANS, we successfully correlated changes in the mesoscopic collective dynamics and microscopic membrane structure upon incorporation of n-alkanes.
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Ladybird beetles are high-mobility insects and explore broad areas by switching between walking and flying. Their excellent wing transformation systems enabling this lifestyle are expected to provide large potential for engineering applications. However, the mechanism behind the folding of their hindwings remains unclear. The reason is that ladybird beetles close the elytra ahead of wing folding, preventing the observation of detailed processes occurring under the elytra. In the present study, artificial transparent elytra were transplanted on living ladybird beetles, thereby enabling us to observe the detailed wing-folding processes. The result revealed that in addition to the abdominal movements mentioned in previous studies, the edge and ventral surface of the elytra, as well as characteristic shaped veins, play important roles in wing folding. The structures of the wing frames enabling this folding process and detailed 3D shape of the hindwing were investigated using microcomputed tomography. The results showed that the tape spring-like elastic frame plays an important role in the wing transformation mechanism. Compared with other beetles, hindwings in ladybird beetles are characterized by two seemingly incompatible properties: (i) the wing rigidity with relatively thick veins and (ii) the compactness in stored shapes with complex crease patterns. The detailed wing-folding process revealed in this study is expected to facilitate understanding of the naturally optimized system in this excellent deployable structure.
Subject(s)
Biomechanical Phenomena/physiology , Coleoptera/anatomy & histology , Wings, Animal/anatomy & histology , Wings, Animal/physiology , Animals , X-Ray MicrotomographyABSTRACT
1,2-Bis(4'-n-alkoxybenzoyl)hydrazine [BABH(n), n is the number of carbon atoms in the alkyl chain] exhibits two different Ia3[combining macron]d cubic phases depending on the chain length (5 ≤n≤ 13 and 15 ≤n≤ 22). The molecular packing modes, not only of molecular cores but also of alkyl chains, are investigated through a maximum entropy method (MEM) and an analysis of the chain-length dependence of the body diagonal of the unit cell. The analyses revealed the difference in molecular packing. The short-chain Ia3[combining macron]d structure of BABH(n) (5 ≤n≤ 13) is constructed by single-layered core motifs and bilayers of alkyl chains, in which the orientation is tilted from the normal to the layer. The long-chain Ia3[combining macron]d structure (15 ≤n≤ 22) is formed by double-layered core motifs and monolayers of alkyl chains, in which the orientation is normal to the layer. Based on the molecular packing modes, the reentrant behavior between the two Ia3[combining macron]d phases was clarified. It was revealed that the alkyl chains of BABH(n) molecules play an essential role in the formation and stability of the two Ia3[combining macron]d structures.
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We investigate the phase separation of a ternary lipid bilayer including n-alkane and construct the ternary phase diagram. When a certain proportion of a long n-alkane is mixed with a binary mixture of lipids, which exhibit the disordered liquid-crystalline phase and the ordered gel phase at room temperature, we observed the characteristic morphology of bilayers with phase separation. The ordered bilayer forms flat and rigid domains, which is connected or rimmed with flexible domains in the disordered phase. The asymmetric emergence of the phase separation region close to the ordered phase side is interpreted based on the almost equal distribution of the n-alkane to the ordered and disordered phase domains.
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Photoinduced changes in the upper critical solution temperature (UCST) were investigated for polymer solutions in an azobenzene-doped liquid crystal solvent. The UCST of poly(methyl methacrylate) (PMMA) and polystyrene (PS) solutions dropped upon irradiation with UV light, which induces trans-cis photoisomerization of the doped azo dye. In the case of PMMA solutions, the photoinduced drop in UCST was significantly larger than that expected from previous studies using azo-based polymers and common solvents. Moreover, the UCST of PS solutions also decreased under photoirradiation, in a direction opposite to that expected from the contribution of polarity. X-ray diffraction data of the solvent suggest that the decreased intermolecular interaction in the solvent (i.e. larger distance between the solvent molecules) is responsible for the photoresponsive behavior of the UCST. The proposed mechanism is consistent with the Flory-Huggins theory. Using such photoresponses in the UCST, the isothermal transition between 2-phase and 1-phase states by photoirradiation was demonstrated.
ABSTRACT
We present herein a method to fabricate a higher-order fiber grating (HOFG) for use as a fiber-cavity mirror in a fiber laser. The HOFG was fabricated by irradiating the Yb-doped large core of a double-clad fiber by a femtosecond pulsed laser. The HOFG served as a laser cavity mirror with a reflectance of 13.2% and yielded a laser line with a spectral full width at half-maximum of 0.56 nm.