Photochromism through excited-state intermolecular proton transfer (ESInterPT) processes based on keto-enol tautomerization was found in phenazine-2,3-diol PD1 and its monoalkoxy derivative PD2 in a glassy matrix at 77 K: the colorless solutions of enol forms PD1-E and PD2-E at 298 K transformed into orange-colored solutions of keto forms PD1-K and PD2-K upon photoirradiation (λ = 385 nm) at 77 K. Furthermore, this report is the first to achieve the single-crystal X-ray structural analyses of phenazine-2,3-diol PD1 and its monoalkoxy derivative PD2, since the report on the synthesis of PD1 70 years ago. Indeed, it was found that PD1 and PD2 molecules exist in the keto form (PD1-K) and the enol form (PD2-E), respectively, in the crystal, and the neighboring PD1-K and PD2-E molecules are linked by one-dimensional intermolecular NHâ¯O and OHâ¯N hydrogen bonding, respectively. The fact suggests strongly that for PD1 and PD2, the formation of continuous intermolecular hydrogen bonding in aggregates such as in a glassy matrix at 77 K is involved in the keto-enol tautomerization of phenazine-2,3-diol derivatives based on ESInterPT. More interestingly, the color and the photoabsorption spectrum of the solids obtained by sublimation of crystals of PD2-E are similar to those for the crystals of PD1-K, indicating that the PD2 molecule exists in the keto form (PD2-K) in the solid of the sublimate. Therefore, this study provides a valuable insight for a greater understanding of the keto-enol tautomerization of diazaacene-diol derivatives and their photophysical properties in the solution and in the solid state.
Soft actuators generate motion in response to external stimuli and are indispensable for soft robots, particularly future miniature robots with complex structure and motion. Similarly to conventional hard robots, electricity is suitable for the stimulation. However, previous electrochemical soft actuators require a tethered connection to a power supply, limiting their size, structure, and motion. Here, wireless electrochemical soft actuators composed of hydrogels and driven by bipolar electrochemistry are reported. Viologen, which dimerizes by one-electron reduction and dissociates by one-electron oxidation, is incorporated in the side chains of the gel networks and works as a reversible cross-link. Wireless and reversible electrochemical actuation of the hydrogels, i.e., muscle-like shrinking and swelling, is demonstrated at microscopic and even macroscopic scales.
Providing standardized, high-quality rehabilitation for critically ill patients is a crucial issue. In 2017, the Japanese Society of Intensive Care Medicine (JSICM) promulgated the "Evidence-Based Expert Consensus for Early Rehabilitation in the Intensive Care Unit" to advocate for the early initiation of rehabilitations in Japanese intensive care settings. Building upon this seminal work, JSICM has recently conducted a rigorous systematic review utilizing the Grading of Recommendations, Assessment, Development, and Evaluation (GRADE) methodology. This endeavor resulted in the formulation of Clinical Practice Guidelines (CPGs), designed to elucidate best practices in early ICU rehabilitation. The primary objective of this guideline is to augment clinical understanding and thereby facilitate evidence-based decision-making, ultimately contributing to the enhancement of patient outcomes in critical care settings. No previous CPGs in the world has focused specifically on rehabilitation of critically ill patients, using the GRADE approach. Multidisciplinary collaboration is extremely important in rehabilitation. Thus, the CPGs were developed by 73 members of a Guideline Development Group consisting of a working group, a systematic review group, and an academic guideline promotion group, with the Committee for the Clinical Practice Guidelines of Early Mobilization and Rehabilitation in Intensive Care of the JSICM at its core. Many members contributed to the development of the guideline, including physicians and healthcare professionals with multiple and diverse specialties, as well as a person who had been patients in ICU. Based on discussions among the group members, eight important clinical areas of focus for this CPG were identified. Fourteen important clinical questions (CQs) were then developed for each area. The public was invited to comment twice, and the answers to the CQs were presented in the form of 10 GRADE recommendations and commentary on the four background questions. In addition, information for each CQ has been created as a visual clinical flow to ensure that the positioning of each CQ can be easily understood. We hope that the CPGs will be a useful tool in the rehabilitation of critically ill patients for multiple professions.
Molecular photoswitches are extensively used as molecular machines because of the small structures, simple motions, and advantages of light including high spatiotemporal resolution. Applications of photoswitches depend on the mechanical responses, in other words, whether they can generate motions against mechanical forces as actuators or can be activated and controlled by mechanical forces as mechanophores. Sterically hindered stiff stilbene (HSS) is a promising photoswitch offering large hinge-like motions in the E/Z isomerization, high thermal stability of the Z isomer, which is relatively unstable compared to the E isomer, with a half-life of ca. 1000 years at room temperature, and near-quantitative two-way photoisomerization. However, its mechanical response is entirely unexplored. Here, we elucidate the mechanochemical reactivity of HSS by incorporating one Z or E isomer into the center of polymer chains, ultrasonicating the polymer solutions, and stretching the polymer films to apply elongational forces to the embedded HSS. The present study demonstrated that HSS mechanically isomerizes only in the Z to E direction and reversibly isomerizes in combination with UV light, i.e., works as a photomechanical hinge. The photomechanically inducible but thermally irreversible hinge-like motions render HSS unique and promise unconventional applications differently from existing photoswitches, mechanophores, and hinges.
The International Commission on Radiological Protection (ICRP) 118th recommendation significantly reduced the threshold dose for cataract development from 8 to 0.5 Gy. Equivalent dose limits for the crystalline lenses of radiation workers are being reviewed for individual countries. Interventional radiology (IR) procedures are less invasive than surgery and have become widespread; however, there are concerns about exposure not only to patients but also to staff, including operators. Therefore, in this study, we used a human phantom to measure the near-lens dose of the operators (cardiologists, neurosurgeons and radiologists) and estimated the operator's lens dose for every major procedure in each clinical department; this was found to vary. Owing to the different imaging and fluoroscopy conditions of each department, and the varying ratio of fluoroscopy to radiography, it is necessary to measure the lens dose for each condition, as in this study. In addition, this study explains the differences between the protective effect of various safety equipment and the appropriate use of protective plates; it can contribute to the reduction of lens doses for operators.
Molecular photoswitches have been widely used as molecular machines in various fields due to the small structures and simple motions generated in reversible isomerization. However, common photoswitches, as represented by azobenzene (AB), cannot combine both large motions and high thermal stability, which are critically important for some practical applications in addition to high photoisomerization yields. Here, we focus on a promising photoswitch, stiff stilbene (SS), and its derivative, sterically hindered SS (HSS). The detailed investigation of their performance with a comparison to AB demonstrated that HSS is an outstanding photoswitch offering larger motions than AB and SS, ca. 90% photoisomerization in both E-to-Z and Z-to-E directions, and significantly high thermal stability with a half-life of ca. 1000 years at room temperature. The superior performance of HSS promises its use in various applications, even where previous photoswitches have troubles and are unavailable.
Stilbenes , Azo Compounds/chemistry
Cumulative dose effects, which are one of the main causes of errors that occur when an implantable cardiac pacemaker (ICP) is irradiated with ionizing radiation, induce permanent failure in ICPs. Although flattening filter free (FFF) beams, which are often used in stereotactic radiotherapy, are known to have different characteristics from conventional (with flattening filter [WFF]) beams, the cumulative dose effects on ICPs with FFF beams have been under-investigated. This study investigates ICP failure induced by cumulative dose effects of FFF beams. When the ICP placed in the center of the irradiation field was irradiated with 10 MV-FFF at 24 Gy/min, the cumulative dose at which failure occurred was evaluated on the basis of the failure criteria associated with high cumulative dose as described in the American Association of Physicists in Medicine Task Group 203. The ICP failures such as a mild battery depletion at a cumulative dose of 10 Gy, pacing-output voltage change >25% at a cumulative dose of 122 Gy, and the loss of telemetry capability at cumulative dose 134 Gy were induced by cumulative dose effects. The cumulative doses by which the cumulative dose effects of FFF beams induced ICP failure were not very different from those reported in previous studies with WFF beams. Therefore, radiotherapy with FFF beams (and WFF beams) for patients with ICP requires appropriate management for minimizing the cumulative dose effects.
Pacemaker, Artificial , Prostheses and Implants , Dose-Response Relationship, Radiation , Electric Impedance
BACKGROUND/AIM: Because current image-guided radiotherapy systems can only correct six axes, it is impossible to correct the twisting of cervical vertebrae. The purpose of this study was to clarify the relationship between cervical vertebrae twisting and cranial angle. MATERIALS AND METHODS: Nineteen patients who underwent intensity-modulated radiation therapy were retrospectively reviewed. Twisting of cervical vertebrae was analysed using planning computed tomography (CT) and megavoltage CT images for image-guided radiotherapy. RESULTS: Although the cranial angle during planning CT was not strongly correlated with twisting (correlation coefficient <0.7), when the patients were divided into two groups by cranial angle, the twisting of the small-angle group was significantly reduced. Specifically, cranial angles of <25° significantly and efficiently reduced the twisting of the upper cervical vertebra compared with those of the other groups. CONCLUSION: Twisting of the upper cervical vertebrae is reduced by using a cranial angle of <25° during planning CT.
Head and Neck Neoplasms , Radiotherapy, Image-Guided , Cervical Vertebrae/diagnostic imaging , Head , Head and Neck Neoplasms/diagnostic imaging , Head and Neck Neoplasms/radiotherapy , Humans , Neck , Retrospective Studies
Background Since the optic pathways are the most vulnerable to radiation, the treatment of skull base tumors involving them is challenging. In this study simulation plans by multi-beam (MB) intensity-modulated radiation therapy (IMRT) and volumetric modulated arc therapy (VMAT), both with the flattened beam (FB) and flattening-filter-free beam (FFF), were compared in terms of covering of the target and sparing of the optic pathways. Materials and methods Treatment planning was simulated by MB-IMRT with FB and FFF and by 2-rotational VMAT with FB and FFF in three cases of skull base meningioma [volume of the planned target volume (PTV; PTV margin=2 mm except for overlapping area with optic pathways or brainstem): 8.6 ml, 34.6 ml, and 55.3 ml respectively], which were treated previously by multi-fractionated MB-IMRT [45 Gy/18 fx. (fraction) with 7-, 6-, and 5-beam] using a conventional Novalis (BrainLAB, Tokyo, Japan) planned by iPlan (BrainLAB, Tokyo, Japan). In all three cases, the optic pathways were adjacent to the lesion. The reference CT with contouring data set of target volumes [gross tumor volume (GTV) and PTV] and OARs (organs at risk) was transferred from iPlan to Eclipse (Varian Medical Systems, Tokyo, Japan). In this study, hypofractionated radiation therapy by 30 Gy/5 fx. was designed; 95% dose (28.5 Gy/5 fx.) was prescribed to D95 (dose to 95% volume of PTV). Conformity index (CI), homogeneity index (HI, D5/D95), D[0.1 ml] (dose to 0.1 ml) for optic pathways, and D[1 ml] for brainstem and eyes, and V[20 Gy] (volume delivered with 20 Gy or more/5 fx.) of the whole brain were evaluated. Results The indices did not differ between FB and FFF, in either MB-IMRT or VMAT. Between MB-IMRT and VMAT, the indices were similar. The mean dose of PTV and HI was a little larger with MB-IMRT than with VMAT. D[0.1 ml] of the optic pathways and D[1 ml] of the ipsilateral eye were smaller with VMAT in all three cases. D[1 ml] of the brainstem was smaller with VMAT in two cases, though it was similar in one case. Conclusion Based on our findings, VMAT with FFF might be the optimal method to treat cases of skull base meningioma involving optic pathways. However, further studies involving more cases are required to arrive at a conclusive verdict.
Direct irradiation may cause malfunctioning of cardiac implantable electronic devices (CIEDs). Therefore, a treatment plan that does not involve direct irradiation of CIEDs should be formulated. However, CIEDs may be directly exposed to radiation because of the sudden intrafractional movement of the patient. The probability of CIED malfunction reportedly depends on the dose rate; however, reports are only limited to dose rates ≤8 Gy/min. The purpose of this study was to investigate the effect of X-ray dose rates >8 Gy/min on CIED function. Four CIEDs were placed at the center of the radiation field and irradiated using 6 MV X-ray with flattening filter free (6 MV FFF) and 10 MV X-ray with flattening filter free (10 MV FFF). The dose rate was 4-14 Gy/min for the 6 MV FFF and 4-24 Gy/min for 10 MV FFF beams. CIED operation was evaluated with an electrocardiogram during each irradiation. Three CIEDs malfunctioned in the 6 MV FFF condition, and all four CIEDs malfunctioned in the 10 MV FFF condition, when the dose rate was >8 Gy/min. Pacing inhibition was the malfunction observed in all four CIEDs. Malfunction occurred simultaneously along with irradiation and simultaneously returned to normal function on stopping the irradiation. An X-ray dose rate >8 Gy/min caused a temporary malfunction due to interference. Therefore, clinicians should be aware of the risk of malfunction and manage patient movement when an X-ray dose rate >8 Gy/min is used for patients with CIEDs.
Defibrillators, Implantable , Heart/radiation effects , Pacemaker, Artificial , Radiotherapy Dosage , X-Rays/adverse effects , Dose-Response Relationship, Radiation , Electric Conductivity , Electrocardiography , Electronics , Equipment Design , Humans , Radiography , Radiotherapy Planning, Computer-Assisted , Radiotherapy, Intensity-Modulated
Tumor locations are commonly delineated by referring to magnetic resonance (MR) images. However, MR images have geometric distortions that cannot be completely corrected. This study aimed to investigate quantitatively uncorrectable error [residual error (RE)] with the use of an open-source plugin for scientific image analysis. The RE values were calculated by Fiji, which was enhanced by Image J image processing software. The results obtained with the open-source plugin for scientific image analysis agreed with the results obtained with the commercially available software. Obtaining detailed geometric distortion data for each facility and device could facilitate safe treatment because the homogeneous magnetic field in MR imaging varies across devices and over time. Therefore, using an open-source plugin for scientific image analysis may be an accurate and effective technique for evaluating the RE of MR imaging systems.
Image Processing, Computer-Assisted/methods , Magnetic Resonance Imaging , Software , Algorithms , Phantoms, Imaging , Tomography, X-Ray Computed
OBJECTIVE: The efficacy of stereotactic radiosurgery (SRS) using Gamma Knife (GK) (Elekta, Tokyo) is well known. Recently, Automatic Brain Metastases Planning (ABMP) Element (BrainLAB, Tokyo) for a LINAC-based radiation system was commercially released. It covers multiple off-isocenter targets simultaneously inside a multi-leaf collimator field and enables SRS / stereotactic radiotherapy (SRT) with a single group of LINAC-based dynamic conformal multi-arcs (DCA) for multiple brain metastases. In this study, dose planning of ABMP (ABMP-single isocenter DCA (ABMP-SIDCA)) for SRS of small multiple brain metastases was evaluated in comparison with those of conventional multi-isocenter DCA (MIDCA-SRS) (iPlan, BrainLAB, Tokyo) and GK-SRS (GKRS). METHODS: Simulation planning was performed with ABMP-SIDCA and GKRS in the two cases of multiple small brain metastases (nine tumors in both), which had been originally treated with iPlan-MIDCA. First, a dosimetric comparison was done between ABMP-SIDCA and iPlan-MIDCA in the same setting of planning target volume (PTV) margin and D95 (dose covering 95% of PTV volume). Second, dosimetry of GKRS with a margin dose of 20 Gy was compared with that of ABMP-SIDCA in the setting of PTV margin of 0, 1 mm, and 2 mm, and D95=100% dose (20 Gy). RESULTS: First, the maximum dose of PTV and minimum dose of gross tumor volume (GTV) were significantly greater in ABMP-SIDCA than in iPlan-MIDCA. Conformity index (CI, 1/Paddick's CI) and gradient index (GI, V (half of prescription dose) / V (prescription dose)) in ABMP-SIDCA were comparable with those of iPlan-MIDCA. Second, PIV (prescription isodose volume) of GKRS was consistent with that of 1 mm margin - ABMP-SIDCA plan in Case 1 and that of no-margin ABMP-SIDCA plan in Case 2. Considering the dose gradient, the mean of V (half of prescription dose) of ABMP-SIDCA was not broad, comparable to GKRS, in either Case 1 or 2. CONCLUSIONS: The conformity and dose gradient with ABMP-SIDCA were as good as those of conventional MIDCA for each lesion. If the conditions of the LINAC system permit a minimal PTV margin (1 mm or less), ABMP-SIDCA might provide excellent dose fall-off comparable with that of GKRS thereby enabling a short treatment time.
