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Aim: The study aimed to quantitatively clarify the effects of several weeks of static stretching on the flexibility of the rectus femoris muscle using shear wave elastography., Material and Methods: Fifteen healthy men (age: 26.4 ± 2.2 years) were instructed to perform 5 min of voluntary static stretching of their right rectus femoris muscles five times a week for four weeks. The participants adjusted their stretching inrectus femoris muscle tensity to a point immediately before experiencing discomfort or pain. The Young's modulus of the rectus femoris muscle and the knee-flexion range of motion were measured as indicators of flexibility. The Young's modulus was measured using shear wave elastography. Measurements were performed at baseline, as well as at two and four weeks after the stretching program started. A generalized linear mixed model was used to assess the change in the Young's modulus after the stretching program and the effects of the Young's modulus on the knee-flexion range of motion., Results: The Young's modulus of the rectus femoris muscle decreased after two and four weeks of stretching compared with the baseline ( p = 0.0004 and p <0.0001, respectively). The Young's modulus of the rectus femoris muscle and the four-week duration of stretching affected the knee-flexion range of motion ( p = 0.0242 and 0.0016, respectively)., Conclusions: Shear wave elastography quantitatively revealed that several weeks of static stretching increased the flexibility of the rectus femoris muscle in healthy men. A four-week static stretching regimen reduced the Young's modulus of the rectus femoris muscle and increased the knee-flexion range of motion., Competing Interests: Conflict of interest The authors do not report any financial or personal connections with other persons or organizations that might negatively affect the contents of this publication and/or claim authorship rights to this publication., (© 2024 Bungo Ebihara et al., published by Sciendo.)

Soft materials that respond to external stimuli are promising candidates for next-generation actuators with human-friendly nature 1,2 . Among various stimuli to induce strain, light offers spatial selectivity, which allows versatile motion of a continuous body. However, spatial selectivity of photoactuation has been limited in two dimension due to the predominant absorption of photons by chromophores near a light source in accordance with Beer-Lambert law. Here, we report the deformation of crosslinked liquid-crystalline polymer films triggered by two-photon absorption. The films containing azotolane moieties show photoinduced deformation upon irradiation with fs laser pulses through two-photon absorption. The direction of photoinduced bending is controlled by depth-selective excitation with a focused laser beam. Furthermore, the mode of deformation is transformed from bending to twisting by irradiating spots near an edge of the film. Inhomogeneous photoirradiation with high spatial selectivity allows an infinite variation of three-dimensional motions even apart from preprogrammed behavior, which would be advantageous especially in application to microactuators., (© 2024. The Author(s).)

Molecule-based hybrid layered magnets provide an ideal platform for investigating the long-range spin-ordering process in low-dimensional magnetic systems. Within this context, a promising area of research is spin-sandwiched hybrid layered magnets. These materials offer the potential to explore how the spin, which is sandwiched between magnetic layers, is influenced by the internal magnetic fields generated by the magnetic layers. Herein, we report a layered ferrimagnet with intercalated biferrocenium ([bifc] + ) radicals, [bifc][{Ru 2 (2,3,5,6-F 4 ArCO 2 ) 4 } 2 (TCNQF 2 )] (1, TCNQF 2 = 2,5-difluorotetracyano- p -quinodimethane). The [{Ru 2 (2,3,5,6-F 4 ArCO 2 ) 4 } 2 (TCNQF 2 )] - moiety acts as a ferrimagnetic layer with S T = 3/2, composed of a paddlewheel [Ru 2 II,II (2,3,5,6-F 4 ArCO 2 ) 4 ] (2,3,5,6-F 4 ArCO 2 - = 2,3,5,6-tetrafluorobenzoate) with S = 1 and 2,5-difluoro-7,7,8,8-tetracyanoquinodimethanate (TCNQF 2 ˙ - ) units with S = 1/2 in a 2 : 1 ratio. The isostructural paramagnetic compound [bifc][{Rh 2 (2,3,5,6-F 4 ArCO 2 ) 4 } 2 (TCNQF 2 )] (2) consisting of diamagnetic [Rh 2 II,II (2,3,5,6-F 4 ArCO 2 ) 4 ] components was also synthesized. An investigation of the properties of 2 revealed minimal magnetic interaction between the [bifc] + and TCNQF 2 ˙ - components. Compound 1 displayed long-range ferrimagnetic ordering at the Curie temperature of 105 K without any frequency dependence on alternating current (AC) susceptibility, due to the combination of predominant ferrimagnetic ordering within the layer and interlayer ferromagnetic dipole interactions. However, subsequent stepwise magnetic ordering involving a strong AC frequency dependence was observed upon further cooling. These dynamic behaviors are associated with the ordering of two types of anisotropic [bifc] + spins between the ferrimagnetic layers, indicating that [bifc] + spin ordering is sensitive to anisotropic internal magnetic fields generated by the ferrimagnetic layers., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Objective: We aimed to clarify the relationship between the changes in echo intensity (EI) and Young's modulus of the soleus (SOL) muscle after ankle fracture surgery., Methods: Sixteen participants after ankle fracture surgery participated in this study (mean age: 46.8 ± 21.4 years). At three and five months after surgery, ankle range of motion (ROM), ankle strength, SOL muscle EI, and Young's modulus were measured, and changes in values were calculated. The EI was measured using the B-mode and ImageJ software (National Institutes of Health, Bethesda, MD), and Young's modulus was measured using shear wave elastography (SWE). The EI values corrected for subcutaneous fat thickness were calculated. Correlation and simple regression analysis were used to clarify the relationship between the amount of change in EI, the amount of change in Young's modulus, and the amount of change in ankle ROM., Results: Simple regression analysis showed that the amount of change in EI influenced the amount of change in Young's modulus of the SOL muscle (r = 0.623; p = 0.010) and the amount of change in ankle dorsiflexion ROM with the knee flexed (r = -0.702; p = 0.002)., Conclusion: The change in EI of the SOL muscle affected the change in Young's modulus after ankle fracture surgery. Clinically, changes in the EI may reflect changes in muscle stiffness., Competing Interests: Human subjects: Consent for treatment and open access publication was obtained or waived by all participants in this study. The Ethics Committee of Tsuchiura Kyodo General Hospital issued approval (2024FY32). The study was conducted in accordance with the Declaration of Helsinki. Animal subjects: All authors have confirmed that this study did not involve animal subjects or tissue. Conflicts of interest: In compliance with the ICMJE uniform disclosure form, all authors declare the following: Payment/services info: All authors have declared that no financial support was received from any organization for the submitted work. Financial relationships: All authors have declared that they have no financial relationships at present or within the previous three years with any organizations that might have an interest in the submitted work. Other relationships: All authors have declared that there are no other relationships or activities that could appear to have influenced the submitted work., (Copyright © 2024, Miyasaka et al.)

Yokoi A, Miyasaka H, Ogawa H, Itoh S, Okazaki H, Sonoda S. Effect of combining an upper limb rehabilitation support robot with task-oriented training on severe upper limb paralysis after spinal cord infarction: A case report. Jpn J Compr Rehabil Sci 2024; 15: 42-48., Objective: This study examined the effect of an upper limb rehabilitation support robot and task-oriented training on treating a patient with severe upper limb paralysis after spinal cord infarction who required total assistance with self-care., Case: A 60-year-old man was diagnosed with watershed infarction in the C5-7 spinal cord region. He was admitted to our hospital 18 days after onset of the disease. The patient had severe paralysis of both upper limbs, and the total score for the Functional Independence Measure (FIM) motor items was 25 points. Regarding the Canadian Occupational Performance Measure (COPM), three goals were listed: "eating," "going to the toilet," and "raising one's hand in a meeting." The performance of "going to the toilet" was rated three points, and the performance and satisfaction of other items were one point. The intervention was practiced for 1 h/day, mainly items selected from COPM. The training using an upper limb rehabilitation support robot was added for 1 h/day. The upper limb rehabilitation support robot adjusted the range of motion and dosage according to the patient's motor function level and recovery status. About three months after admission, he improved until his upper limbs could be held in space on activities of daily living (ADL), and the total score for the FIM motor items improved to 81 points. The satisfaction and performance of all items listed as goals in COPM at the time of admission improved to ten points, and the patient was discharged 108 days after admission., Conclusions: The upper limb rehabilitation support robot training that matched the level of motor function improved the motor function and active range of motion (ROM). ADL generalization through task-oriented training helped improve self-care. The use of COPM for the training to enable the patient to acquire the ability to perform meaningful activities led to improved COPM performance and satisfaction., Competing Interests: Conflict of Interests: The authors have no conflict of interest directly relevant to the content of this article., (©2024 Kaifukuki Rehabilitation Ward Association.)

Background: Diabetic macular edema (DME) causes vision impairment and significant vision loss. Portable optical coherence tomography (OCT) has the potential to enhance the accessibility and frequency of DME screening, facilitating early diagnosis and continuous monitoring. This study aimed to evaluate the reliability of a portable OCT device (ACT100) in assessing DME compared with a traditional stationary OCT device (Cirrus 5000 HD-OCT plus). Methods: This prospective clinical investigation included 40 eyes of 33 patients with DME. Participants with significant refractive errors (myopia > -6.0 diopters or hyperopia > +3.0 diopters), vitreous hemorrhage, tractional retinal detachment, or other ocular diseases affecting imaging were excluded. Spectral-domain OCT was performed by a single examiner using both devices to capture macular volume scans under mydriasis. Central macular thickness (CMT) was evaluated using the analysis software for each device: Cirrus used version 6.0.4, and ACT100 used version V20. We analyzed inter-evaluator and inter-instrument agreements for qualitative assessments of the intraretinal fluid (IRF), subretinal fluid (SRF), and epiretinal membrane (ERM) using Cohen's kappa coefficient, whereas quantitative CMT assessments were correlated using Spearman's correlation coefficient. Results: Substantial inter-evaluator agreement for IRF/SRF (κ = 0.801) and ERM (κ = 0.688) with ACT100 and inter-instrument agreement (κ = 0.756 for IRF/SRF, κ = 0.684 for ERM) were observed. CMT values measured using ACT100 were on average 29.6 μm lower than that of Cirrus (285.8 ± 56.6 vs. 315.4 ± 84.7 μm, p < 0.0001) but showed a strong correlation (R = 0.76, p < 0.0001). Conclusions: ACT100 portable OCT demonstrated high reliability for DME evaluations, comparable to that of stationary systems.

Objective: Although shear-wave elastography (SWE) can be used to assess muscle stiffness, SWE assessments are expensive. Echo intensity (EI) is an indicator of muscle quality and can potentially be used to assess muscle stiffness. This study aimed to determine the relationship between the EI and Young's modulus of the soleus (SOL) muscle after ankle fracture surgery., Methods: Eighteen participants who had undergone ankle fracture surgery were evaluated (mean age: 48.8 ± 20.6 years). Three months post-surgery, Young's modulus and EI of the SOL muscle were measured using SWE and the combination of B-mode ultrasound and ImageJ software, respectively. EI and Young's modulus measurements were obtained with the participant kneeling with knees bent 90°, upper body supported on a table, and ankles dorsiflexed 10°. The regions of interest used to measure EI and Young's modulus were identical. The EI value corrected for the subcutaneous fat thickness was also calculated. Pearson's correlation coefficients were calculated to examine the relationship of Young's modulus with the uncorrected and corrected EI., Results: Although the uncorrected EI was correlated with Young's modulus of the SOL muscle (r = 0.567; p = 0.014), the corrected EI showed a stronger correlation (r = 0.637; p = 0.005). High intra-rater was also found reliability for the EI and Young's modulus measurements of the SOL muscle in participants after ankle fracture surgery., Conclusions: The EI and Young's modulus of the SOL muscle were positively correlated. In particular, the corrected EI showed a stronger correlation with Young's modulus than the uncorrected EI. Clinically, EI measurements may facilitate objective evaluation of muscle stiffness., Competing Interests: Human subjects: Consent was obtained or waived by all participants in this study. The Ethics Committee of Tsuchiura Kyodo General Hospital issued approval with reference number 2024FY32. Animal subjects: All authors have confirmed that this study did not involve animal subjects or tissue. Conflicts of interest: In compliance with the ICMJE uniform disclosure form, all authors declare the following: Payment/services info: All authors have declared that no financial support was received from any organization for the submitted work. Financial relationships: All authors have declared that they have no financial relationships at present or within the previous three years with any organizations that might have an interest in the submitted work. Other relationships: All authors have declared that there are no other relationships or activities that could appear to have influenced the submitted work., (Copyright © 2024, Miyasaka et al.)

The increased anthropogenic emission level of CO 2 urges the development of CO 2 -responsive materials, but is it possible to regulate the inherent electronic properties through weak physisorption of a ubiquitous gas such as CO 2 ? Herein, we intended to answer this imperative question by the first case of CO 2 -actuated variable spin-state stabilisation in an interdigitated Hofmann-type coordination polymer [Fe II Pd(CN) 4 L 2 ] (1, L = methyl isonicotinate), showing a wide shift in transition temperature ( T eq ) from 178 K at P CO 2 = 0 kPa to 229 K at P CO 2 = 100 kPa. Interestingly, the emergence of a stepped behaviour in the heating process below P CO 2 = 10 kPa and overlapping magnetic susceptibility values above P CO 2 = 10 kPa elucidate the selective LS state stabilisation solely correlated with the extent of CO 2 accommodation. Based on the magnetic response and phase transition diagrams obtained under respective P CO 2 , a plausible scenario of the spin-state switching can be interpreted as (1 ls + ) → (1 hs + ) → 1 hs at P CO 2 ≤ 10 kPa, → 1 hs at 100 kPa < P CO 2 ≥ 32 kPa and → → 1 hs at 100 kPa, where 1 and 1' represent CO 2 -free and CO 2 -encapsulated states, respectively. The cooperative CO 2 sorption with SCO based on the varied CO 2 pressure corroborates a novel case for developing CO 2 -responsive magnetic materials henceforth., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Understanding physicochemical property changes based on reaction kinetics is required to design materials exhibiting desired functions at arbitrary timings. In this work, we investigated the photodimerization of anthracene derivatives in single crystals. Single crystals of 9-cyanoanthracene (9CA) and 9-anthraldehyde (9AA) exhibited reaction front propagation on the optical length scale, while 9-methylanthracene and 9-acetylanthracene crystals underwent spatially homogeneous conversion. Moreover, the sigmoidal behavior in the absorbance change associated with the reaction was much pronounced in the case of 9CA and 9AA and correlated with the observation of heterogeneous reaction progress. A kinetic analysis based on the Finke-Watzky model showed that the effective quantum yield of the photochemical reaction changes by more than an order of magnitude during the course of the reaction in 9CA and 9AA. Both the reaction front propagation and nonlinear kinetic behavior could be rationalized in terms of the difference in the cooperativity of the reactions. We propose a plausible mechanism for the heterogeneous reaction progress in single crystals that depends on the magnitude of the conformational change required for reaction. Our results provide useful information to understand the connection between photochemical reaction progress in the crystalline phase and the dynamic changes in the physicochemical properties., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Background: Recent studies have suggested that N-methyl-D-aspartate (NMDA) receptors are involved in the cell proliferation in several tumors. However, there have been no reports demonstrating the expression of NR1 subunit of the NMDA receptor in large cell neuroendocrine carcinoma (LCNEC)., Case Presentation: Here, we report the first elderly case of paraneoplastic anti-NMDA receptor encephalitis associated with LCNEC of the lung with NR1 expression. Of note, NR1 subunit expression in the tumor cells of the present case was confirmed by immunohistochemistry (IHC). Radiation therapy and immunotherapies, such as corticosteroids and intravenous immunoglobulin (IVIG), shrank the tumors and improved neurological symptoms in the present case. Additionally, we also confirmed the expression of NR1 in the tumor cells obtained from three other cases with LCNEC of the lung at our hospital by IHC., Conclusion: Our IHC results indicate that LCNEC generally expresses NR1 subunit and NMDA receptor may be involved in the tumor development and growth., (© 2024. The Author(s).)

Optical coherence tomography (OCT) is an indispensable instrument in ophthalmology; however, some facilities lack permanent OCT devices. ACT100, a portable SD-OCT system, allows for medical examinations at hospitals that do not have OCT and house calls. We investigated the usefulness of ACT100 by examining the reproducibility of retinal thickness measurements in 35 healthy participants with normal eyes using ACT100 and Cirrus. Using two OCTs, the OCT imaging of both eyes of each subject was performed. Macular retinal thickness was evaluated using the average value in nine lesions of the Early Treatment Diabetic Retinopathy Study (ETDRS) circle. Both models captured images in all cases. In the right eye, mean retinal thickness was significantly lower than in the ACT100 group in all regions; however, the measured values correlated well. The intraclass correlation coefficients showed the same high reliability as the Cirrus. The coefficients of variation (CVs) of both models showed little variation and high stability; however, the CV of ACT100 was significantly higher. The left eye was almost identical. Macular retinal thickness measured using ACT100 showed slightly greater variability than that by Cirrus; the reproducibility was good and correlated well with that of Cirrus. This technique is a suitable alternative to conventional OCT.

The effect of whole-body vibration (WBV) stretching on soleus (SOL) muscle stiffness remains unclear. Therefore, we aimed to investigate the acute and long-term effects of stretching with WBV on SOL muscle stiffness. This study employed a repeated-measures experimental design evaluating 20 healthy young males. SOL muscle stretching with WBV was performed for 5 min per day (1 min per set, five sets) over 4 weeks, for 4 days a week. Participants stretched the SOL muscle with ankle dorsiflexion in a loaded flexed knee position on a WBV device. Data were obtained to examine acute effects before stretching, immediately after stretching, and at 5, 10, 15, and 20 min. Moreover, data were obtained to examine the long-term effects before stretching, immediately after the completion of the 4-week stretching program, and at 2 and 4 weeks later. SOL muscle stiffness was measured using Young's modulus with shear wave elastography. The acute effect of SOL muscle stretching with WBV persisted for up to 20 min. Additionally, the long-term effect of stretching was better maintained than the acute effect, which was effective for up to 4 weeks ( p < 0.001). Clinically, continuous stretching with WBV may be used to improve SOL muscle stiffness in rehabilitation programs.

Polycyclic aromatic hydrocarbons (PAHs) are fragments of graphene that have attracted considerable attention as a new class of carbon-based materials. The functionalization of edge positions in PAHs is important to enable the modulation of physical and chemical properties essential for various applications. However, straightforward methods that combine functional group tolerance and regioselectivity remain sought after. Here we report a photochemical approach for the direct alkylation of carbon-hydrogen bonds in PAHs that takes place in a regiospecific manner, an outcome that has never been achieved in related thermal reactions. A reaction mechanism involving a single electron transfer process from photo-excited PAHs to sulfones, and a rationale for the origin of regioselectivity are proposed on the basis of spectroscopic analyses and theoretical calculations., Competing Interests: The authors declare no conflicts of interest., (This journal is © The Royal Society of Chemistry.)

Background: Stiffness of the soleus muscle (SOL) and Achilles tendon (AT) are associated with Achilles tendinitis and medial tibial stress syndrome. Therefore, reliable SOL and AT stiffness measurements are important for monitoring clinical progress. However, little is known about the absolute reliability of the stiffness measurements of SOL and AT in different ankle positions. This study aimed to determine the absolute reliability of the Young's modulus measurements of the SOL and AT in different ankle positions in healthy young males., Methods: This study included 33 healthy young males. SOL and AT stiffnesses were measured using Young's modulus and shear-wave elastography (SWE). Measurements were taken while the participants were kneeling, with their knees flexed to 90°, and the upper body supported by a table. Ultrasound images were recorded at ankle dorsiflexion angles of -10°, 0°, and 10°. The same measurements were repeated 15 min after the first measurement. Bland-Altman plots were used to verify the type or amount of error and 95 % confidence interval of the minimal detectable change (MDC 95 ) values of the measurements., Results: Bland-Altman plots identified that there was no fixed or proportional bias and that there was good agreement between the first- and second-time measurements of the SOL and AT, respectively, among all angles. The MDC 95 of the Young's modulus of SOL at -10°, 0°, and 10° of ankle dorsiflexion were 5.6 kPa, 7.0 kPa, and 10.1 kPa, respectively, and AT were 15.8 kPa, 16.4 kPa, and 17.8 kPa, respectively., Conclusion: Young's modulus measurements of the SOL and AT using SWE can be used to quantify elastic properties with high confidence. Clinically, assessing changes in the Young's moduli of the SOL and AT using SWE may help determine the effectiveness of interventions., Competing Interests: The authors declare no conflict of interest., (© 2024 Asia Pacific Knee, Arthroscopy and Sports Medicine Society. Published by Elsevier (Singapore) Pte Ltd.)

Herein, we introduce a model of electronic spin isomers, the electronic counterpart of nuclear spin isomers, by using a stable organic diradical. The diradical, composed of two benzotriazinyl radicals connected by a rigid triptycene skeleton, exhibits a small singlet-triplet energy gap of -3.0 kJ/mol, indicating ca. 1:1 coexistence of the two spin states at room temperature. The diradical shows characteristic near-IR absorption bands, which are absent in the corresponding monoradical subunit. Variable temperature measurements revealed that the absorbance of the NIR band depends on the abundance of the singlet state, allowing us to identify the NIR band as the singlet-specific absorption band. It enables photoexcitation of one of the two spin states coexisting in thermal equilibrium. Transient absorption spectroscopy disclosed that the two spin states independently follow qualitatively different excited-state dynamics. These results demonstrate a novel approach to the design and study of electronic spin isomers based on organic diradicals., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The optimal time to ambulation remains unclear for intensive care unit (ICU) patients following abdominal surgery. While previous studies have explored various mobilization techniques, a direct comparison between ambulation and other early mobilization methods is lacking. Additionally, the impact of time to ambulation on complications and disuse syndrome prevention requires further investigation. This study aimed to identify the optimal time to ambulation for ICU patients after abdominal surgery and considered its potential influence on complications and disuse syndrome. We examined the relationship between time to ambulation and hospital length of stay (LOS). Patients were categorized into the nondelayed (discharge within the protocol time) and delayed (discharge later than expected) groups. Data regarding preoperative functioning, postoperative complications, and time to discharge were retrospectively collected and analyzed. Of the 274 postsurgical patients managed in the ICU at our hospital between 2018 and 2020, 188 were included. Time to ambulation was a significant prognostic factor for both groups, even after adjusting for operative time and complications. The area under the curve was 0.72, and the cutoff value for time to ambulation was 22 h (sensitivity, 68%; specificity, 77%). A correlation between time to ambulation and complications was observed, with both impacting the hospital LOS (model 1: p < 0.01, r = 0.22; model 2: p < 0.01, r = 0.29). Specific cutoff values for time to ambulation will contribute to better surgical protocols.

The resonance between an electronic transition of a micro/nanoscale object and an incident photon flux can modify the radiation force exerted on that object, especially at an interface. It has been theoretically proposed that a non-linear stimulated emission process can also induce an optical force, however its direction will be opposite to conventional photon scattering/absorption processes. In this work, we experimentally and theoretically demonstrate that a stimulated emission process can induce a repulsive pulling optical force on a single trapped dye-doped particle. Moreover, we successfully integrate both attractive pushing (excited state absorption) and repulsive pulling (stimulated emission) resonance forces to control the overall exerted optical force on an object, validating the proposed non-linear optical resonance theory. Indeed, the results presented here will enable the optical manipulation of the exerted optical force with exquisite control and ultimately enable single particle manipulation., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Iron(ii) spin cross-over (SCO) compounds combine a thermally driven transition from the diamagnetic low-spin (LS) state to the paramagnetic high-spin (HS) state with a distinct change in the crystal lattice volume. Inversely, if the crystal lattice volume was modulated post-synthetically, the spin state of the compound could be tunable, resulting in the inverse effect for SCO. Herein, we demonstrate such a spin-state tuning in a breathing cyanido-bridged porous coordination polymer (PCP), where the volume change resulting from guest-induced gate-opening and -closing directly affects its spin state. We report the synthesis of a three-dimensional coordination framework {[Fe II (4-CNpy) 4 ] 2 [W IV (CN) 8 ]·4H 2 O} n (1·4H 2 O; 4-CNpy = 4-cyanopyridine), which demonstrates a SCO phenomenon characterized by strong elastic frustration. This leads to a 48 K wide hysteresis loop above 140 K, but below this temperature results in a very gradual and incomplete SCO transition. 1·4H 2 O was activated under mild conditions, producing the nonporous {[Fe II (4-CNpy) 4 ] 2 [W IV (CN) 8 ]} n (1) via a single-crystal-to-single-crystal process involving a 7.3% volume decrease, which shows complete and nonhysteretic SCO at T 1/2 = 93 K. The low-temperature photoswitching behavior in 1 and 1·4H 2 O manifested the characteristic elasticity of the frameworks; 1 can be quantitatively converted into a metastable HS state after 638 nm light irradiation, while the photoactivation of 1·4H 2 O is only partial. Furthermore, nonporous 1 adsorbed CO 2 molecules in a gated process, leading to {[Fe II (4-CNpy) 4 ] 2 [W IV (CN) 8 ]·4CO 2 } n (1·4CO 2 ), which resulted in a 15% volume increase and stabilization of the HS state in the whole temperature range down to 2 K. The demonstrated post-synthetic guest-exchange employing common gases is an efficient approach for tuning the spin state in breathing SCO-PCPs., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Miyasaka H, Nakagawa Y, Okazaki H, Sonoda S. Influence of sitting posture on anterior buttock sliding during wheelchair propulsion of hemiplegic stroke patients. Jpn J Compr Rehabil Sci 2023; 14: 54-59., Objectives: This study investigated the influence of different sitting postures on wheelchair propulsion ability., Methods: The subjects were stroke patients who scored at least 2 points on the Stroke Impairment Assessment Set for abdominal muscle strength and trunk verticality and 3 points for non-paralytic side lower-limb muscle strength. Moreover, the patients were divided by their everyday wheelchair propulsion posture: Lean on Back Support (LBS); n = 8), those who leaned their back against the back support; and non-LBS ( n = 11), those who moved their back away from the back support. For the wheelchair propulsion method, straight one-hand, one-leg propulsion was used on the non-paralyzed side for 10 m, followed by turning around a target 3 m ahead on each of the paralyzed and non-paralyzed sides. We then compared the propulsion times, number of propulsions, and difference in length from the front end of the patella on the non-paralyzed side to the front end of the seat surface (buttock sliding distance) between the groups., Results: The buttock sliding distance was significantly shorter in the non-LBS group than in the LBS group in the paralyzed and non-paralyzed side turning tasks ( p < 0.05). Propulsion times, number of propulsions, and grip strength did not differ significantly between the groups., Conclusion: Even in patients with good trunk function, propulsion while leaning against the back support can easily result in anterior buttock sliding, leading to a secondary risk of injury. These results suggest that it is necessary to provide guidance on the propulsion posture and seating to hold the trunk vertically to minimize anterior sliding during propulsion., Competing Interests: Conflict of Interest: The authors have no conflict of interest directly relevant to the content of this article., (©Kaifukuki Rehabilitation Ward Association 2023.)

The effects of lipopolysaccharide (LPS) from Rhodobacter sphaeroides , a purple non-sulfur bacterium (PNSB), on the gene expression of the root of rice ( Oryza sativa ) were investigated by next generation sequencing (NGS) RNA-seq analysis. The rice seeds were germinated on agar plates containing 10 pg/mL of LPS from Rhodobacter sphaeroides NBRC 12203 (type culture). Three days after germination, RNA samples were extracted from the roots and analyzed by RNA-seq. The effects of dead (killed) PNSB cells of R. sphaeroides NBRC 12203 T at the concentration of 10 1 cfu/mL (ca. 50 pg cell dry weight/mL) were also examined. Clean reads of NGS were mapped to rice genome (number of transcript ID: 44785), and differentially expressed genes were analyzed by DEGs. As a result of DEG analysis, 300 and 128 genes, and 86 and 8 genes were significantly up- and down-regulated by LPS and dead cells of PNSB, respectively. The plot of logFC (fold change) values of the up-regulated genes of LPS and PNSB dead cells showed a significant positive relationship (r 2 = 0.6333, p < 0.0001), indicating that most of the effects of dead cell were attributed to those of LPS. Many genes related to tolerance against biotic (fungal and bacterial pathogens) and abiotic (cold, drought, and high salinity) stresses were up-regulated, and the most strikingly up-regulated genes were those involved in the jasmonate signaling pathway, and the genes of chalcone synthase isozymes, indicating that PNSB induced defense response against biotic and abiotic stresses via the jasmonate signaling pathway, despite the non-pathogenicity of PNSB.

Background and Objective : Achilles tendon (AT) stiffness can reduce ankle dorsiflexion. However, whether AT stiffness affects the ankle dorsiflexion angle at a maximum squat depth remains unclear. Therefore, we aimed to investigate the relationship between the Young's modulus of the AT and ankle dorsiflexion angle at the maximum squat depth in healthy young males using shear-wave elastography (SWE). Materials and Methods : This cross-sectional study included 31 healthy young males. AT stiffness was measured using the Young's modulus through SWE. The ankle dorsiflexion angle at the maximum squat depth was measured as the angle between the vertical line to the floor and the line connecting the fibula head and the lateral malleolus using a goniometer. Results : Multiple regression analysis identified the Young's modulus of the AT at 10° of ankle dorsiflexion (standardized partial regression coefficient [ β ] = -0.461; p = 0.007) and the ankle dorsiflexion angle in the flexed knee ( β = 0.340; p = 0.041) as independent variables for the ankle dorsiflexion angle at maximum squat depth. Conclusions : The Young's modulus of the AT may affect the ankle dorsiflexion angle at the maximum squat depth in healthy young males. Therefore, improving the Young's modulus of the AT may help increase the ankle dorsiflexion angle at maximum squat depth.

The phenomenon of crystal melting by light irradiation, known as photo-induced crystal-to-liquid transition (PCLT), can dramatically change material properties with high spatiotemporal resolution. However, the diversity of compounds exhibiting PCLT is severely limited, which hampers further functionalisation of PCLT-active materials and the fundamental understandings of PCLT. Here, we report on heteroaromatic 1,2-diketones as the new class of PCLT-active compounds, whose PCLT is based on conformational isomerisation. In particular, one of the diketones demonstrates luminescence evolution prior to crystal melting. Thus, the diketone crystal exhibits dynamic multistep changes in the luminescence colour and intensity during continuous ultraviolet irradiation. This luminescence evolution can be ascribed to the sequential PCLT processes of crystal loosening and conformational isomerisation before macroscopic melting. Single-crystal X-ray structural analysis, thermal analysis, and theoretical calculations of two PCLT-active and one inactive diketones revealed weaker intermolecular interactions for the PCLT-active crystals. In particular, we observed a characteristic packing motif for the PCLT-active crystals, consisting of an ordered layer of diketone core and a disordered layer of triisopropylsilyl moieties. Our results demonstrate the integration of photofunction with PCLT, provide fundamental insights into the melting process of molecular crystals, and will diversify the molecular design of PCLT-active materials beyond classical photochromic scaffolds such as azobenzenes., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Magnetism of layered magnets depends on the inter-layer through-space magnetic interactions ( J NNNI ). Using guest sorption to address inter-layer pores in bulk-layered magnets is an efficient approach to magnetism control because the guest-delicate inter-layer distance ( l trans ) is a variable parameter for modulating J NNNI . Herein, we demonstrated magnetic changes induced by the adsorption of CO 2 , N 2 , and O 2 gases in various isostructural layered magnets with a π-stacked pillared-layer framework, , (M = Co, 1, Fe, 2, Cr, 3; Cp* = η 5 -C 5 Me 5 ; 2,3,5,6-F 4 PhCO 2 - = 2,3,5,6-tetrafluorobenzoate; TCNQ = 7,7,8,8-tetracyano- p -quinodimethane). Each compound had almost identical adsorption capability for the three types of gases; only CO 2 adsorption was found to have a gated profile. A breathing-like structural modulation involving the extension of l trans occurred after the insertion of gases into the isolated pores between the [Ru 2 ] 2 -TCNQ ferrimagnetic layers, which is more significant for CO 2 than for O 2 and N 2 , due to the CO 2 -gated transition. While adsorbent 1 with M = Co ( S = 0) was an antiferromagnet with T N = 75 K, 1⊃CO 2 was a ferrimagnet with T C = 76 K, whereas 1⊃N 2 and 1⊃O 2 were antiferromagnets with T N = 68 K. The guest-insertion effect was similarly confirmed in 2 and 3, and was characteristically dependent on the type of sandwiched spin in as M = Fe ( S = 1/2) and Cr ( S = 3/2), respectively. This study reveals that common gases such as CO 2 , O 2 , and N 2 can serve as crucial triggers for the change in magnetism as a function of variable parameter l trans ., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The effects of seed bio-priming (seed soaking) with purple non-sulfur bacteria (PNSB) on the grain productivity and root development of rice were examined by a field study and laboratory experiments, respectively. Two PNSB strains, Rhodopseudomonas sp. Tsuru2 and Rhodobacter sp. Tsuru3, isolated from the paddy field of the study site were used for seed bio-priming. For seed bio-priming in the field study, the rice seeds were soaked for 1 day in water containing a 1 × 10 5 colony forming unit (cfu)/mL of PNSB cells, and the rice grain productivities at the harvest time were 420, 462 and 504 kg/are for the control, strain Tsuru2-primed, and strain Tsuru3-primed seeds, respectively. The effects of seed priming on the root development were examined with cell pot cultivation experiments for 2 weeks. The total root length, root surface area, number of tips and forks were evaluated with WinRhizo, an image analysis system, and strains Tsuru2- and Tsuru3-primed seeds showed better root development than the control seeds. The effects of seed priming with the dead (killed) PNSB cells were also examined, and the seed priming with the dead cells was also effective, indicating that the effects were attributed to some cellular components. We expected the lipopolysaccharide (LPS) of PNSB as the effective component of PNSB and found that seed priming with LPS of Rhodobacter sphaeroides NBRC 12203 (type culture) at the concentrations of 5 ng/mL and 50 ng/mL enhanced the root development.

The coordination polymers (CPs) with binary ligands, including 2,5-dihydroxy-1,4-benzoquinone (H2DHBQ) and 4,4'-bipyridyl (bpy), were synthesized using in situ hydrolysis of 2,5-dimethoxy-1,4-benzoquinone (DMBQ). Three kinds of CPs were obtained depending on the metal ions. For M = Mn and Zn, a 1D zigzag chain structure with cis conformation ( cis -1D-M ) was obtained, whereas Co, Ni, and Cu compounds afforded a 2D net structure with trans conformation ( trans -2D-M ) with a 1D pore. A linear chain structure was also obtained for M = Cu. Magnetic susceptibility (χ M T ) at 300 K in cis -1D-Mn and trans -2D-Co was evaluated to be 4.421 and 2.950 cm 3 K mol -1 , respectively, indicating that both compounds are in the high-spin state. According to the N 2 adsorption isotherms at 77 K, trans -2D-Ni showed microporosity with the BET surface area of 177 m 2 g -1 , whereas the isomorphic trans -2D-Co rarely adsorbed N 2 at 77 K. This phenomenon was explained by the difference of diffusion kinetics of the adsorbent molecules, which was supported by the CO 2 adsorption isotherms at 195 K. The optical band gaps of cis -1D-Mn , cis -1D-Zn , trans -2D-Co , and trans -2D-Ni were estimated to be 1.6, 1.8, 1.0, and 1.1 eV, respectively, by using UV-vis-NIR spectroscopy., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Background: The difference in the effects of combined therapy with repetitive facilitative exercise (RFE) and neuromuscular electrical stimulation (NMES) on stroke upper limb paralysis was only reported by a pilot study; it has not been investigated in many patients., Objective: We investigated the effect of combined therapy with RFE and NMES on stroke patients with severe upper paresis., Methods: This study included 99 of the very severe paresis stroke patients with scores of zero or 1a in the Finger-Function test of the Stroke Impairment Assessment Set (SIAS). We randomly divided the patients into four groups, namely, NMES, RFE, RFE under NMES, and conventional training (CT) groups. A total of 20 min of group-specific training in addition to 40 min of conventional exercise per day, seven times a week for 4 weeks after admission, was performed. The upper extremity items of the Fugl-Meyer Assessment (FMA) were evaluated before and after the training period., Results: The total score gains of the FMA, FMA wrist item, and FMA finger item were significantly larger in the RFE under NMES group than those in the CT group ( p < 0.05)., Conclusion: The combination of voluntary movement and electrical stimulation may promote the activation of paralyzed muscles and improve distal function for very severe paralyzed upper limbs., Competing Interests: The authors declare that there is no conflict of interest regarding the publication of this paper., (Copyright © 2022 Hitoshi Ohnishi et al.)

Helically twisted conductive nanocarbon materials are applicable to optoelectronic and electromagnetic molecular devices working on the nanometer scale. Herein, we report the synthesis of per-peri-perbenzo[5]- and [9]helicenes in addition to previously reported π-extended [7]helicene. The homogeneously π-extended helicenes can be regarded as helically fused oligo-phenanthrenes. The HOMO-LUMO gap decreased significantly from 2.14 to 1.15 eV with increasing helical length, suggesting the large effective conjugation length (ECL) of the π-extended helical framework. The large ECL of π-extended helicenes is attributed to the large orbital interactions between the phenanthrene subunits at the 9- and 10-positions, which form a polyene-like electronic structure. Based on the experimental results and DFT calculations, the ultrafast decay dynamics on the sub-picosecond timescale were attributed to the low-lying conical intersection., (© 2022. The Author(s).)

Rhodobacter sphaeroides , a purple non-sulfur photosynthetic bacterium (PNSB), was disrupted by sonication and fractionated by centrifugation into the supernatant and pellet. The effects of the supernatant and pellet on plant growth were examined using Brassica rapa var. perviridis (komatsuna) in the pot experiments. Both fractions showed growth-promoting effects: the supernatant at high concentrations (1 × 10 7 to 4 × 10 7 cfu-equivalent mL -1 ) and the pellet at a low concentration of 2 × 10 3 cfu-equivalent mL -1 ). We expected lipopolysaccharide (LPS) to be the active principle of the pellet fraction and examined the effects of LPS on the growth of B. rapa var. perviridis . The growth of the plants was significantly enhanced by the foliar feeding of R. sphaeroides LPS at concentrations ranging from 10 to 100 pg mL -1 . The present study is the first report indicating that LPS acts as one of the active principles of the plant-growth-promoting effect of PNSB.

Purple non-sulfur bacteria (PNSB) are used as probiotics in shrimp aquaculture; however, no studies have examined the probiotic effects of PNSB in shrimp at the gene expression level. In this study, we examined the effects of a marine PNSB, Rhodovulum sulfidophilum KKMI01, on the gene expression of kuruma shrimp ( Marsupenaeus japonicus ). Short-term (3 days) effects of R. sulfidophilum KKMI01 on the gene expression in shrimp were examined using small-scale laboratory aquaria experiments, while long-term (145 days) effects of R. sulfidophilum KKMI01 on the growth performance and gene expression were examined using 200-ton outdoor aquaria experiments. Gene expression levels were examined using qRT-PCR. Results of the short-term experiments showed the upregulation of several molting-related genes, including cuticle proteins, calcification proteins, and cuticle pigment protein, suggesting that PNSB stimulated the growth of shrimp. The upregulation of several immune genes, such as prophenoloxidase, antimicrobial peptides, and superoxide dismutase, was also observed. In the 145-day outdoor experiments, the average body weight at harvest time, survival rate, and feed conversion ratio were significantly improved in PNSB-treated shrimp, and upregulation of molting and immune-related genes were also observed. When PNSB cells were added to the rearing water, the effective dosage of PNSB was as low as 10 3 cfu/mL, which was more than a million times dilution of the original PNSB culture (2-3 × 10 9 cfu/mL), indicating that R. sulfidophilum KKMI01 provides a feasible and cost-effective application as a probiotic candidate in shrimp aquaculture.

Because supramolecular polymerization of emissive π-conjugated molecules depends strongly on π-π stacking interaction, the formation of well-defined one-dimensional nanostructures often results in a decrease or only a small increase of emission efficiency. This is also true for our barbiturate-based supramolecular polymers wherein hydrogen-bonded rosettes of barbiturates stack quasi-one-dimensionally through π-π stacking interaction. Herein we report supramolecular polymerization-induced emission of two regioisomeric 2,3-diphenylthiophene derivatives functionalized with barbituric acid and tri(dodecyloxy)benzyl wedge units. In CHCl 3 , both compounds are molecularly dissolved and accordingly poorly emissive due to a torsion-induced non-radiative decay. In methylcyclohexane-rich conditions, these barbiturates self-assemble to form crystalline nanofibers and exhibit strongly enhanced emission through supramolecular polymerization driven by hydrogen-bonding. Our structural analysis suggests that the barbiturates form a tape-like hydrogen-bonding motif, which is rationalized by considering that the twisted geometries of 2,3-diphenylthiophene cores prevend the competing rosettes from stacking into columnar supramolecular polymers. We also found that a small difference in the molecular polarity originating from the substitutional position of the thiophene core influences interchain association of the supramolecular polymers, affording different luminescent soft materials, gel and nanosheet., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Here, we present single crystalline capsules of a photoresponsive molecule produced by simple recrystallization from organic solutions without direct human processing. During the crystal growth process, a movie was taken of the capsule taking in the organic solution. The capsules responded rapidly (<1 s) to the UV light stimuli and released the captured solution or solute. In principle, they can take in any substance dissolved in organic solvents, and their size can be controlled. Moreover, the capsule can be broken by multi-photon excitation using a near-infrared laser within the biological window. Furthermore, because the molecular packing in the crystal is unidirectional, the response can be controlled by the polarization of the light. This study shows the new potential of photoresponsive molecules., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The electrocyclic reaction dynamics of a photochromic dithiazolylarylene derivative, 2,3-dithiazolylbenzothiophene (DTA) was investigated by using time-resolved transient absorption and fluorescence spectroscopies. The closed-ring isomer of DTA undergoes cycloreversion through the conical intersection mediating the potential energy surfaces of the excited and ground states, which is in agreement with the Woodward-Hoffmann rules for the electrocyclic reactions of 6π electron systems. On the other hand, a large portion of the open-ring isomer undergoes cyclization along the distinct reaction scheme, in which the cyclization takes place in the excited state manifold leading to the formation of the excited state of the closed-ring isomer. The suppression of the geometrical motion of DTA due to the intramolecular interaction could open a new efficient reaction pathway resulting in the formation of the electronically excited state of the product., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Molecular materials whose electronic states are multiply varied depending on external stimuli are among the most promising targets for the development of multiply accessible molecular switches. Here, we report a honeycomb layer composed of tetraoxolene-bridged iron (Fe) subunits whose charge-ordered states are multiply variable via thermal treatments and solvation/desolvation with the crystallinity intact. The compound is (NPr 4 ) 2 [Fe 2 (Cl 2 An) 3 ] ( 1-d ; NPr 4 + = tetra- n -propylammonium; Cl 2 An 2- = 2,5-dichloro-3,6-dihydroxo-1,4-benzoquinonate), which possesses three charge-ordered states: a low-temperature (LT) phase [(Fe 3+ ) 2 (Cl 2 An 2- )(Cl 2 An˙ 3- ) 2 ] 2- ; an intermediate (IM) phase [(Fe 2.5+ ) 2 (Cl 2 An 2- )(Cl 2 An 2.5- ) 2 ] 2- ; and a high-temperature (HT) phase [(Fe 2+ ) 2 (Cl 2 An 2- ) 3 ] 2- that varies according to temperature. In addition, the LT phase of 1-d is reversibly changeable to another IM phase in its solvated compound 1 via a solvation/desolvation process at room temperature. This example demonstrates a new multiple-switching system based on electron transfer and host-guest chemistry in a charge-flexible metal-organic framework., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The reaction dynamics of excited-state intramolecular proton transfer (ESIPT) of 2,2'-dihydroxyazobenzene (2,2'-DHAB) was investigated by means of white-light supercontinuum femtosecond transient absorption spectroscopy. A coherent in-phase oscillation was observed in the entire wavelength range where stimulated emission of the photoproduct is dominant. This result indicates that the transition strength of the product state is dynamically modulated by a nuclear wavepacket motion (non-Condon effect). The observed vibration was assigned to the mode which modulates the distance between oxygen and hydrogen atoms. By integrating the result of time-dependent density functional theory calculation, the origin of the non-Condon effect was attributed to a dynamical change of configuration interaction between enol and keto characters along the vibrational coordinate, indicating that this vibration is strongly related to the reaction coordinate of ESIPT.

Visible-light sensitized photoswitches have been paid particular attention in the fields of life sciences and materials science because long-wavelength light reduces photodegradation, transmits deep inside of matters, and achieves the selective excitation in condensed systems. Among various photoswitch molecules, the phenoxyl-imidazolyl radical complex (PIC) is a recently developed thermally reversible photochromic molecule whose thermal back reaction can be tuned from tens of nanoseconds to tens of seconds by rational design of the molecular structure. While the wide range of tunability of the switching speed of PIC opened up various potential applications, no photosensitivity to visible light limits its applications. In this study, we synthesized a visible-light sensitized PIC derivative conjugated with a benzil unit. Femtosecond transient absorption spectroscopy revealed that the benzil unit acts as a singlet photosensitizer for PIC by the Dexter-type energy transfer. Visible-light sensitized photochromic reactions of PIC are important for expanding the versatility of potential applications to life sciences and materials science., (Copyright © 2019, Kobayashi et al.; licensee Beilstein-Institut.)

Rehabilitation and mobility training of post-stroke patients is crucial for their functional recovery. While traditional methods can still help patients, new rehabilitation and mobility training methods are necessary to facilitate better recovery at lower costs. In this work, our objective was to design and develop a rehabilitation training system targeting the functional recovery of post-stroke users with high efficiency. To accomplish this goal, we applied a bilateral training method, which proved to be effective in enhancing motor recovery using tactile feedback for the training. One participant with hemiparesis underwent six weeks of training. Two protocols, "contralateral arm matching" and "both arms moving together", were carried out by the participant. Each of the protocols consisted of "shoulder abduction" and "shoulder flexion" at angles close to 30 and 60 degrees. The participant carried out 15 repetitions at each angle for each task. For example, in the "contralateral arm matching" protocol, the unaffected arm of the participant was set to an angle close to 30 degrees. He was then requested to keep the unaffected arm at the specified angle while trying to match the position with the affected arm. Whenever the two arms matched, a vibration was given on both brachialis muscles. For the "both arms moving together" protocol, the two arms were first set approximately to an angle of either 30 or 60 degrees. The participant was asked to return both arms to a relaxed position before moving both arms back to the remembered specified angle. The arm that was slower in moving to the specified angle received a vibration. We performed clinical assessments before, midway through, and after the training period using a Fugl-Meyer assessment (FMA), a Wolf motor function test (WMFT), and a proprioceptive assessment. For the assessments, two ipsilateral and contralateral arm matching tasks, each consisting of three movements (shoulder abduction, shoulder flexion, and elbow flexion), were used. Movements were performed at two angles, 30 and 60 degrees. For both tasks, the same procedure was used. For example, in the case of the ipsilateral arm matching task, an experimenter positioned the affected arm of the participant at 30 degrees of shoulder abduction. The participant was requested to keep the arm in that position for ~5 s before returning to a relaxed initial position. Then, after another ~5-s delay, the participant moved the affected arm back to the remembered position. An experimenter measured this shoulder abduction angle manually using a goniometer. The same procedure was repeated for the 60 degree angle and for the other two movements. We applied a low-cost Kinect to extract the participant's body joint position data. Tactile feedback was given based on the arm position detected by the Kinect sensor. By using a Kinect sensor, we demonstrated the feasibility of the system for the training of a post-stroke user. The proposed system can further be employed for self-training of patients at home. The results of the FMA, WMFT, and goniometer angle measurements showed improvements in several tasks, suggesting a positive effect of the training system and its feasibility for further application for stroke survivors' rehabilitation.