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.

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.

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.

Effects of the loss and reconstruction of molar occlusal support on memory retrieval and hippocampal neuron density in rats.

PURPOSE: Animal experiments have shown that the loss of occlusal support causes impairments in spatial cognition. Many reports have focused on the memory encoding process, and only few studies have investigated the effect on memory retrieval. This study aimed to examine the effects of both the loss and reconstruction of occlusal support on the memory retrieval process and on the number of hippocampal pyramidal cells. METHODS: The experimental animals were divided into a molarless group, in which molars were extracted, a denture-wearing molarless group with experimental dentures inserted after molar extraction, and a control group. Radial maze trials were performed for 20 consecutive days (acquisition phase). The rats were tested on long-term memory retention following the acquisition phase in eight trials every five days, and in an additional trial 20 days later (probe phase). RESULTS: The denture-wearing molarless group showed higher levels of spatial learning and memory than the molarless group. There were no significant differences in memory retrieval during the probe phase between the denture-wearing molarless and the control group. The molarless group showed significantly worse spatial learning and memory and had fewer neurons in the hippocampus than the control group. CONCLUSIONS: Our results suggest that the loss of occlusal support decreases the number of pyramidal cells in the hippocampus and impairs memory decoding and retrieval. However, this effect is suppressed by the reconstruction of occlusal support.

A new posture measurement method for measuring intrinsic standing posture.

AIMS: Although body posture in relation to the dental condition has been of great interest in the dental profession, rumination bias has been a substantial obstacle to achieving a reliable objective evaluation of the intrinsic body posture. The aim of this study was to establish a posture control protocol that would minimize the effect of bias. METHODOLOGY: Fifteen healthy male volunteers (23-33 years of age) participated in this study. The posture movement was recorded for 10 seconds by a three-dimensional motion capture system. The experiment was performed on four different days. RESULTS: The posture was most stable at 4-5 seconds after the start of the front bulb gaze (the mean coefficient of variation ranged from 0.1 to 44.1). The intraclass correlation coefficients for four days were 0.871-0.975 (P < or = 0.001). CONCLUSIONS: It was concluded that the use of this measurement method helped in producing a reliable intrinsic standing posture where unbiased evaluation of the effect of any intervention on the body posture is researched.

Memory-related gene expression profile of the male rat hippocampus induced by teeth extraction and occlusal support recovery.

OBJECTIVES: The present study aimed to identify the effect of memory-related genes on male rats tested for spatial memory with either molar teeth extraction or its restoration by occlusal support using experimental dentures. DESIGN: Memory-related genes were detected from hippocampi of male Wistar rats (exposed to teeth extraction with or without dentures, or no extraction (control)) (7-week old) after behavioural testing (via the radial maze task) using a DNA microarray. The time course of the expression of these genes was evaluated by quantitative real-time polymerase chain reaction (PCR) (on 49-week-old rats). RESULTS: In preliminary experiments, to determine which memory genes are affected by spatial memory training, DNA microarray analysis revealed that thyrotropin-releasing hormone (Trh) and tenascin XA (Tnxa) were up-regulated and neuronatin (Nnat) and S100a9 were down-regulated after the maze training. The expression of Tnxa, Nnat and S100a9 of 49-week-old rats (during the time course) via quantitative real-time PCR was consistent with the results of microarrays of the preliminary experiment. Expression of Trh that was evaluated by quantitative real-time PCR did not agree with the results for this gene from the microarray for all groups. Therefore, expression of Trh may have increased in only young, trained rats. The expression of S100a9 prior to the maze task was down-regulated in only the extraction group. CONCLUSION: These results demonstrated that Trh, Tnxa and Nnat genes were affected according to the degree of memory in male rats. This study also indicated that S100a9 is a memory-related gene, which is affected by the presence of occlusal support.

Dependence of psychophysical threshold on rate of applied force to the upper first molar in humans.

OBJECTIVE: The study aims to investigate the dynamic perception of a force applied to the upper first molar for different rates of force increase. DESIGN: Six volunteers (four male and two female; mean age, 27.2±2.4 years) with full natural dentition (except for the third molars) participated in this study. The psychophysical threshold for a force applied to the right maxillary first molar and the reaction time corresponding to each threshold were measured for rate of force increase of 103.74, 236.23, 354.58, 478.22 and 584.63 mNs(-1). The physical impulse, which is the integral of force over time, was calculated for each threshold. RESULTS: Psychophysical thresholds in the upper first molar increased with the rate of force increase. The reaction time corresponding to each threshold decreased with increasing force rate. Impulses corresponding to each threshold were independent of force rate. CONCLUSIONS: In the present study, the psychophysical threshold for a force applied to a molar tooth was shown to change depending on the rate of increase of the exerted force. From the viewpoint of the impulse, the dissipated energy necessary to reach the psychophysical sensation threshold was almost constant, regardless of the rate of force increase.

Mechanomyographic activity in the human lateral pterygoid muscle during mandibular movement.

The activity of the lateral pterygoid muscle has been regarded to be related to the pathological condition of the temporomandibular joint (TMJ) in the craniomandibular disorders. Because the lateral pterygoid muscle is a deep muscle, a needle electrode is necessary for EMG recordings. The purpose of this study was to establish a non-invasive method for the evaluation of muscle activity of the lateral pterygoid muscle using mechanomyogram (MMG). In three male subjects, surface electromyogram (EMG) in the left masseter muscle, left anterior and posterior belly of the temporal muscle, left anterior belly of the digastric muscle and needle EMG of the inferior head of the lateral pterygoid were recorded during mandibular movement tasks simultaneously with the MMG derived from a condenser microphone in the external ear canal. There were significant positive correlations between the needle EMG signal of the lateral pterygoid muscle and the MMG signal for the tasks of static jaw opened position of 30 mm of interincisal distance (p=0.000, R(2)=0.725), static jaw opened position of 40 mm of interincisal distance (p=0.000, R(2)=0.753), 5mm protruded mandibular position (p=0.000, R(2)=0.653), the most protruded mandibular position (p=0.000, R(2)=0803). On the contrary, for the task of maximal clenching, there was no significant correlation between the EMG signal of the lateral pterygoid muscle and the MMG signal. These results suggest that the activity of the lateral pterygoid muscle could be evaluated by the MMG signals recorded in the external ear canal, unless jaw closing major muscles show active contraction.