Synthesis and Characterization of Quinone Compounds Derived from Doubly and Triply Linked Diporphyrins and Tuning of Their Absorption Properties.

Porphyrins are attracting increasing attention in materials science and photochemistry owing to their unique properties and diverse applications. This study focuses on modifying and tuning the absorption properties of porphyrins, specifically those of quinoidal porphyrins, to extend their spectral range into the near-infrared (NIR) region. We report the synthesis and structural and physical properties of quinone compounds derived from doubly and triply linked diporphyrins and their metal complexes. Doubly linked diporphyrinquinone exhibits broad panchromatic absorption properties in solution owing to its low symmetry. Metal complexation markedly extends its absorption range into the near-infrared region. In contrast, the metal complexes of the triply linked diporphyrinquinones exhibit sharp and strong absorption bands in the visible to near-infrared region owing to their higher symmetry. The longest absorption wavelength of the triply linked diporphyrinquinones was approximately 1500 nm, which was significantly more red-shifted than that of the doubly linked ones.

On-shelf circulation of warm water toward the Totten Ice Shelf in East Antarctica.

The Totten Glacier in East Antarctica, with an ice volume equivalent to >3.5 m of global sea-level rise, is grounded below sea level and, therefore, vulnerable to ocean forcing. Here, we use bathymetric and oceanographic observations from previously unsampled parts of the Totten continental shelf to reveal on-shelf warm water pathways defined by deep topographic features. Access of warm water to the Totten Ice Shelf (TIS) cavity is facilitated by a deep shelf break, a broad and deep depression on the shelf, a cyclonic circulation that carries warm water to the inner shelf, and deep troughs that provide direct access to the TIS cavity. The temperature of the warmest water reaching the TIS cavity varies by ~0.8 °C on an interannual timescale. Numerical simulations constrained by the updated bathymetry demonstrate that the deep troughs play a critical role in regulating ocean heat transport to the TIS cavity and the subsequent basal melt of the ice shelf.

Relationship between hand stereotypies and purposeful hand use and factors causing skin injuries and joint contractures in individuals with Rett syndrome.

BACKGROUND: Skin injuries and joint contractures in the upper limbs are observed in approximately 50 % of individuals with Rett syndrome, respectively. AIMS: To investigate the relationship between stereotypic hand movements and purposeful hand skills, items related to these, and factors that cause upper extremity skin injuries and joint contractures in individuals with Rett syndrome. STUDY DESIGN: We conducted a cross-sectional observational study in 2020 with families belonging to either of the two largest Rett syndrome organizations in Japan. SUBJECTS: In 2020, we sent a questionnaire to 194 Japanese families. OUTCOME MEASURES: We used descriptive statistics to indicate frequency in each question. We analysed the association between hand stereotypies and purposeful hand use, their associations with each questionnaire item, and the relationship between the occurrence of skin injuries and joint contractures. RESULTS: We acquired information from 72 cases. We found correlations between stereotypy frequency with reaching and between purposeful hand use with intellectual development grade and hand function. Hand and finger skin injuries and elbow and finger joint contractures were associated with wringing/washing, grasping, locomotion, reaching, and intellectual development grade. We identified cut-off points for the occurrence of elbow and finger joint contractures of 10 years 6 months, ability to roll over, finger feeds only, and understanding of simple words. CONCLUSIONS: Direct interventions can reduce hand stereotypies and increase purposeful hand use, while related items can be addressed with indirect interventions. Evaluations of factors that cause skin injuries and joint contractures can prevent their occurrence.

Effect of tranexamic acid administration on intraoperative blood loss during peritonectomy: a single-center retrospective observational study.

BACKGROUND: The efficacy of tranexamic acid in elective major invasive abdominal surgeries has not yet been established. We investigated the effect of tranexamic acid administration on intraoperative blood loss during peritoneal resection of pseudomucinoma and cancerous peritoneal dissemination. METHODS: Patients aged ≥ 20 years old who underwent peritoneal resection for pseudomucinoma or cancerous peritoneal dissemination at the Kishiwada Tokushukai Hospital were included in this single-center retrospective observational study. The tranexamic acid group received 1000 mg of tranexamic acid at the start of the operation, while the control group received the same intraoperative management as the tranexamic acid group, except for the tranexamic acid administration. The primary endpoint was intraoperative blood loss, and a multivariate analysis of the contributing factors was performed. RESULTS: The median volume of intraoperative blood loss was 1372 [interquartile range, 842 - 1877] mL and 907 [516 - 1537] mL in the control and tranexamic acid groups, respectively (p < 0.01). The total volume of blood transfusion during the operation was 2040 [1480 - 2380] mL and 1560 [1000 - 2120] mL in the control and tranexamic acid groups, respectively (p = 0.02). Postoperative blood test results revealed D-dimer values of 7.5 [4.1 - 10.7] µg/mL and 1.8 [1.0 - 3.3] µg/mL in the control and tranexamic acid groups, respectively (p < 0.01). Multivariate analysis showed that tranexamic acid administration was significantly associated with decreased intraoperative blood loss (p = 0.02). CONCLUSION: Tranexamic acid administration may be useful in reducing intraoperative blood loss and blood transfusion volume during highly-invasive surgeries such as peritoneal resection of pseudomucinoma and cancerous peritoneal dissemination.

Relationship between reaction time variability on go/no go tasks and neuropsychological functioning in younger and older adults.

INTRODUCTION: Early detection of cognitive impairment in older adults is important for the prevention of dementia. Intra-individual variability in reaction time (IIV-RT) during go/no-go tasks can be used for the early detection of cognitive impairment in older adults living in the community. This study aimed to determine the relationship between IIV-RT and cognitive function during go/no-go tasks and the cutoff values for determining the risk of cognitive impairment in community-dwelling older adults. METHODS: This study included 31 older adults without cognitive impairment, 15 community-dwelling older adults with cognitive impairment, and 34 healthy young adults. All participants performed a go/no-go task to assess the IIV-RT. Additionally, older adults underwent neuropsychological testing. Based on the results of the Japanese version of the Montreal Test of Cognitive Abilities (MoCA-J), older adults were divided into those with normal cognition and those with cognitive impairment. RESULTS: There were significant differences in the IIV-RT among groups, including a higher IIV in the cognitively impaired group than in young adults and cognitively normal older adults. Moreover, the IIV-RT was correlated with the MoCA-J (r = -0.531, p < 0.001), Trail Making Test Part A (r = 0.571, p < 0.001), and Verbal Fluency Test scores (r = -0.442, p = 0.002). Receiver operating curve analysis showed that the area under the curve for IIV-RT was 0.935, and the cutoff value at which the IIV-RT identified cognitive impairment was 25.37%. CONCLUSIONS: These findings indicate that the IIV-RT during go/no-go tasks is a useful early indicator of cognitive impairment in community-dwelling older adults.

Generation of a BAC transgenic mouse strain that expresses CreERT and a fluorescent protein under the transcriptional control of the Fzd5 locus.

BACKGROUND: The expression of FZD5 distinguishes immature human mesenchymal stem/stromal cells (MSC) in cultures, and the function of FZD5 is crucial for maintaining the proliferation and multilineage differentiation capacity of human MSC. We herein investigated whether Fzd5 expression also marks undifferentiated MSC in animals. METHODS: We generated a transgenic mouse strain (Fzd5-CreERT-tFP635) that expresses CreERT and the fluorescent protein, TurboFP635 (tFP635), under the transcriptional control of the Fzd5 gene using the BAC transgenic technique, and identified cells expressing tFP635 by flow cytometry. We also conducted lineage tracing with this strain. RESULTS: In the bone marrow of transgenic mice, tFP635 was preferentially expressed in MSC, Leptin receptor-expressing MSC (LepR+MSCs), and some Pdgfrα+ Sca1+ MSC (PαS). Inducible lineage tracing using the Fzd5-CreERT-tFP635; CAG-CAT-EGFP strain at the adult stage showed that Fzd5-expressing cells and their descendants labeled with GFP were progressively dominant in LepR+MSC and PαS, and GFP+ cells persisted for 1 year after the activation of CreERT. Adipocyte progenitor cells (APCs), osteoblast progenitor cells (OPCs), and Cd51+ stromal cells were also labeled with GFP. CONCLUSIONS: Our transgenic mouse marks two different types of MSC, LepR+MSC and PαS.

Different brain activation patterns in the prefrontal area between self-paced and high-speed driving tasks.

The purpose of this study was to investigate the effects on prefrontal cortex brain activity when participants attempted to stop a car accurately at a stop line when driving at different speeds using functional near-infrared spectroscopy (fNIRS). Twenty healthy subjects with driving experience drove their own cars for a distance of 60 m five times each at their own pace or as fast as possible. The variation in the distance between the stop line and the car was not significantly different between the self-paced and high-speed tasks. However, oxygenated hemoglobin concentration in the prefrontal cortex was significantly higher in the high-speed task than in the self-paced task. These findings suggest that driving at high speed requires more divided attention than driving at self-paced speed, even though the participants were able to stop the car at the same distance from the target. This study shows the advantages and usefulness of fNIRS .

Comparison of the presence and absence of an intervention to reduce hand stereotypies in individuals with Rett syndrome.

BACKGROUND: We investigated how many individuals with Rett syndrome were undergoing interventions to reduce stereotypic hand movements and the factors determining the presence or absence of an intervention. METHOD: A questionnaire was sent to 194 families. Each survey item was compared between the intervention and non-intervention groups according to the presence or absence of interventions to reduce hand stereotypies. RESULTS: Information was acquired from 72 cases; 72.1% of individuals had received an intervention to reduce stereotypies at some point in their lives. An upper limb splint was the most common intervention. Age, locomotor and reaching function, diagnostic age, frequency and type of stereotypy, joint contractures and stereotypy-associated problems separated the presence or absence of a current or past intervention. CONCLUSIONS: Interventions for stereotypy-associated problems are important and there are several variables related to whether an intervention is received.

Multidecadal poleward shift of the southern boundary of the Antarctic Circumpolar Current off East Antarctica.

The southern boundary (SB) of the Antarctic Circumpolar Current, the southernmost extent of the upper overturning circulation, regulates the Antarctic thermal conditions. The SB's behavior remains unconstrained because it does not have a clear surface signature. Revisited hydrographic data from off East Antarctica indicate full-depth warming from 1996 to 2019, concurrent with an extensive poleward shift of the SB subsurface isotherms (>50 km), which is most prominent at 120°E off the Sabrina Coast. The SB shift is attributable to enhanced upper overturning circulation and a depth-independent frontal shift, generally accounting for 30 and 70%, respectively. Thirty years of oceanographic data corroborate the overall and localized poleward shifts that are likely controlled by continental slope topography. Numerical experiments successfully reproduce this locality and demonstrate its sensitivity to mesoscale processes and wind forcing. The poleward SB shift under intensified westerlies potentially induces multidecadal warming of Antarctic shelf water.

Estimation of Effect of Radiation Dose Reduction for Internal Exposure by Food Regulations under the Current Criteria for Radionuclides in Foodstuff in Japan Using Monitoring Results.

This study examined the effect of food regulations under the current criteria (e.g., 100 Bq/kg for general foods) established approximately a year after the Fukushima Dai-ichi Nuclear Power Plant (FDNPP) accident. Foods are monitored to ensure that foods exceeding the standard limit are not distributed; ~300,000 examinations per year have been performed especially since FY2014. This study comprehensively estimated the internal exposure dose resulting from the ingestion of foods containing radioactive cesium using the accumulated monitoring results. Committed effective dose was conservatively calculated as the product of the radioactive concentration randomly sampled from test results, food intake, and dose coefficient. The median, 95th, and 99th percentile of the dose were 0.0479, 0.207, and 10.6 mSv/y, respectively, in the estimation with all test results (without regulation), and 0.0430, 0.0790, and 0.233 mSv/y, respectively, in the estimation with results within the standard limits (with regulation) in FY2012. In FY2016, the dose with and without regulation were similar, except for high percentile, and those doses were significantly smaller than 1 mSv/y, which was adopted as the basis for the current criteria. The food regulation measures implemented in Japan after the FDNPP accident have been beneficial, and food safety against radionuclides has been ensured.

2019 Diagnostic criteria for mixed connective tissue disease (MCTD): From the Japan research committee of the ministry of health, labor, and welfare for systemic autoimmune diseases.

OBJECTIVE: To update and revise the diagnostic criteria for mixed connective tissue disease (MCTD) issued by the Japan Research Committee of the Ministry of Health, Labor, and Welfare (MHLW), a round table discussion by experts from rheumatology, dermatology, and pediatric medicine was conducted in multiple occasions. METHODS: The definition of MCTD, and items included in the diagnostic criteria were generated by consensus method and evaluation using clinical data of typical and borderline cases of MCTD, by applying to the diagnostic criteria for MCTD proposed in 1996 and 2004 by the Research Committee of MHLW. RESULTS: To the end, all committee members reached consensus. Then, the criteria were assessed in an independent validation cohort and tested against preexisting criteria. The revised criteria facilitate an understanding of the overall picture of this disease by describing the concept of MCTD, common manifestations, immunological manifestation and characteristic organ involvement. Conditions with characteristic organ involvement include pulmonary arterial hypertension, aseptic meningitis and trigeminal neuropathy. Even if the overlapping manifestations are absent, MCTD can be diagnosed based on the presence of the characteristic organ involvement. Furthermore, the criteria were validated for applicability in actual clinical cases, and public comments were solicited from the Japan College of Rheumatology and other associated societies. CONCLUSION: After being reviewed through public comments, the revised diagnostic criteria have been finalized.

Single versus dual pathways to functional outcomes in schizophrenia: Role of negative symptoms and cognitive function.

BACKGROUND: The functional outcomes for many patients with schizophrenia remain poor, and the specific determinants for and pathways to functional outcomes are not well understood to date. It is unknown whether major determinants of outcomes are achieved via a motivated single pathway or by the motivation and capacity defined in dual pathways. This study investigated whether different aspects of functional outcomes, such as residential, social, and vocational outcomes, are the main determinants of the experience factors for negative symptoms or whether the experience factors and cognitive function are the determinants. METHOD: We enrolled 107 patients with schizophrenia. The Social Functioning Scale domains were used to examine whether a single or dual pathway is appropriate for each domain based on the model fit using structural equation modeling. RESULTS: The model goodness of fit criterion showed a dual pathway for residential and vocational outcomes. In contrast, social and recreational outcomes showed a single pathway. CONCLUSION: The major determinants were clearly different for each outcome. Therefore, we emphasize the importance of using different treatment strategies for each outcome. Irrespective of the factors approached, social and recreational outcomes should ultimately focus on motivation. The findings also suggest that interventions should be combined for vulnerable cognitive functions and motivational interventions for residential and vocational outcomes.

Effects of a dual task and different levels of divided attention on motor-related cortical potential.

[Purpose] The aim of this study was to investigate the effect of divided attention on motor-related cortical potential (MRCP) during dual task performance while the difficulty of the secondary task was altered. [Participants and Methods] Twenty-two right-handed healthy volunteers participated in the study. MRCPs were recorded during two tasks, a single task (ST) and a simple (S-DT) or complex dual task (C-DT). The ST involved a self-paced tapping task in which the participants extended their right index finger. In the dual task, the participants performed the ST and a visual number counting task simultaneously. [Results] The amplitude and integral value of MRCP from electroencephalography electrode C3 was significantly higher in the S-DT than in the ST, whereas they were similar between the C-DT and the ST. Medium-load divided attention (i.e., S-DT) led to significantly more changes in the MRCP magnitude than did low-load divided attention (i.e., ST). However, the MRCP of high-load divided attention (i.e., C-DT) was similar to that of low-load divided attention. [Conclusion] These results suggest that MRCP reflects the function of or network between the supplementary motor area and the dorsolateral prefrontal cortex, and may serve as a marker for screening the capacity of individuals to perform dual tasks.

Comprehensive Analysis of Antibodies Induced by Vaccination with 4 Kinds of Avian Influenza H5N1 Pre-Pandemic Vaccines.

Four kinds of avian-derived H5N1 influenza virus, A/Vietnam/1194/2004 (Clade 1), A/Indonesia/5/2005 (Clade 2.1), A/Qinghai/1A/2005 (Clade 2.2), and A/Anhui/1/2005 (Clade 2.3), have been stocked in Japan for use as pre-pandemic vaccines. When a pandemic occurs, these viruses would be used as vaccines in the hope of inducing immunity against the pandemic virus. We analyzed the specificity of antibodies (Abs) produced by B lymphocytes present in the blood after immunization with these vaccines. Eighteen volunteers took part in this project. After libraries of Ab-encoding sequences were constructed using blood from subjects vaccinated with these viruses, a large number of clones that encoded Abs that bound to the virus particles used as vaccines were isolated. These clones were classified into two groups according to the hemagglutination inhibition (HI) activity of the encoded Abs. While two-thirds of the clones were HI positive, the encoded Abs exhibited only restricted strain specificity. On the other hand, half of the HI-negative clones encoded Abs that bound not only to the H5N1 virus but also to the H1N1 virus; with a few exceptions, these Abs appeared to be encoded by memory B cells present before vaccination. The HI-negative clones included those encoding broadly cross-reactive Abs, some of which were encoded by non-VH1-69 germline genes. However, although this work shows that various kinds of anti-H5N1 Abs are encoded by volunteers vaccinated with pre-pandemic vaccines, broad cross-reactivity was seen only in a minority of clones, raising concern regarding the utility of these H5N1 vaccine viruses for the prevention of H5N1 pandemics.

Synthesis of Porphyrinquinone and Doubly-Fused Diporphyrin Quinone Through Oxidation of Diarylporphyrins Using a Hypervalent Iodine Compound.

Treatment of a meso-diarylporphyrin with PhI(OAc)2 in the presence of BF3 ⋅ OEt2 and propionic acid affords the corresponding porphyrinquinone in a high yield (91%). A novel quinone derived from meso-meso ß-ß doubly-fused diporphyrin was obtained as the sole byproduct (16% yield), which exhibits strong panchromatic absorption between 300 and 1000 nm. It has a low HOMO-LUMO gap owing to expanded and low-symmetry π-planes.

Strong ice-ocean interaction beneath Shirase Glacier Tongue in East Antarctica.

Mass loss from the Antarctic ice sheet, Earth's largest freshwater reservoir, results directly in global sea-level rise and Southern Ocean freshening. Observational and modeling studies have demonstrated that ice shelf basal melting, resulting from the inflow of warm water onto the Antarctic continental shelf, plays a key role in the ice sheet's mass balance. In recent decades, warm ocean-cryosphere interaction in the Amundsen and Bellingshausen seas has received a great deal of attention. However, except for Totten Ice Shelf, East Antarctic ice shelves typically have cold ice cavities with low basal melt rates. Here we present direct observational evidence of high basal melt rates (7-16 m yr-1) beneath an East Antarctic ice shelf, Shirase Glacier Tongue, driven by southward-flowing warm water guided by a deep continuous trough extending to the continental slope. The strength of the alongshore wind controls the thickness of the inflowing warm water layer and the rate of basal melting.

Negative symptoms in schizophrenia: Modeling the role of experience factor and expression factor.

Negative symptoms in schizophrenia can be explained by two factors, experience and expression, which should be considered as separate symptoms. However, their relative role in real world functioning has not been clarified. This study aimed to clarify the relative role of experience and expression in real world functioning, and their associations with positive symptoms and neurocognitive function. In total 107 patients with schizophrenia were enrolled. The Social Function and the Brief Negative Symptom Scales were used to evaluate the real world functioning and negative symptoms, respectively. The analysis showed that the expression factor influenced real world functioning through the experience factor. In addition, neurocognitive function affected real world functioning independent of expression and experience. These results suggested that interventions that enhance the communicative expression, such as oxytocin therapy and SST, could successfully be combined with motivational interventions, such as the cognitive behavioral therapy. In addition, real world functioning could be improved by separately performing interventions to compensate for vulnerabilities in neurocognitive function and motivation.

Measurement of complex refractive index with tunable extreme ultraviolet high harmonic source.

We report a broadband refractive index measurement method based on a higher harmonic generation tabletop coherent extreme ultraviolet source. We measured the complex refractive index of a sample material by measuring the interference pattern produced by a bare double slit and comparing this with the pattern produced by another double slit with one slit covered by the sample material. We validated the method by measuring the complex refractive index of aluminum in the photon energy range of 63-78 eV using a neon gas jet. The measurement system had errors of less than 0.02%.

Variation factors of stereotypical hand movements in subjects with Rett syndrome.

Background: Stereotypical hand movements have been observed in most individuals diagnosed with Rett syndrome. Objectives: To investigate factors that increase or decrease hand stereotypies in individuals with Rett syndrome. Methods: A questionnaire regarding hand stereotypies or purposeful hand behaviours was sent to 1016 schools for special needs education and 204 facilities in Japan. Results: Information was acquired from 216 cases (3-53 years old) with Rett syndrome; 81.9% and 87.6% of individuals had factors that increased and decreased stereotypical hand movements, respectively. Stereotypies were mainly increased by displeasure (63.8%) or pleasure (48.5%), and decreased by somnolence (43.5%), pleasure (30.0%), or food (24.1%). Conclusion: Emotion was the main factor increasing stereotypical hand movements, whereas there were a large number of factors that decreased these movements. The factors that decrease stereotypies could be useful to prevent the skin problems or joint contracture observed in patients with Rett syndrome.

Three Types of Broadly Reacting Antibodies against Influenza B Viruses Induced by Vaccination with Seasonal Influenza Viruses.

We analyzed the antibody (Ab) repertoire against influenza B viruses induced by vaccination with seasonal influenza viruses in one individual who had never been vaccinated until 2009. The vaccine used in this study comprised B/Massachusetts/2/2012 (Yamagata lineage), A/Texas/50/2012 (H3N2), and A/California/7/2009 (H1N1). One month after the subject received two vaccinations, blood (200 ml) was obtained and peripheral mononuclear cells were prepared, and a large Ab library was constructed using phage display technology. The library was screened with HA-enriched fraction of B/Massachusetts/2/2012 and B/Brisbane/60/2008 (Victoria lineage) virus, and a total of 26 Abs that potentially bound to hemagglutinin (HA) molecules were isolated. Their binding activities to six influenza B viruses, three of Yamagata lineage and three of Victoria lineage, and two influenza A viruses, H1N1 and H3N2, were examined. The Abs showed cross-reactivity at three different levels. The first type bound to all Yamagata lineage viruses. The second type bound to both Yamagata and Victoria lineage viruses. The third type bound to both influenza A and B viruses. These results indicate that common epitopes exist on HA molecules of influenza virus at various levels, and humans have capability to produce Abs that bind to such common epitopes.