Halogen-Free π $\upi$ -Conjugated Polymers Based on Thienobenzobisthiazole for Efficient Nonfullerene Organic Solar Cells: Rational Design for Achieving High Backbone Order and High Solubility.

In π $\upi$ -conjugated polymers, a highly ordered backbone structure and solubility are always in a trade-off relationship that must be overcome to realize highly efficient and solution-processable organic photovoltaics (OPVs). Here, it is shown that a π $\upi$ -conjugated polymer based on a novel thiazole-fused ring, thieno[2',3':5,6]benzo[1,2-d:4,3-d']bisthiazole (TBTz) achieves both high backbone order and high solubility due to the structural feature of TBTz such as the noncovalent interlocking of the thiazole moiety, the rigid and bent-shaped structure, and the fused alkylthiophene ring. Furthermore, based on the electron-deficient nature of these thiazole-fused rings, the polymer exhibits deep HOMO energy levels, which lead to high open-circuit voltages (VOC s) in OPV cells, even without halogen substituents that are commonly introduced into high-performance polymers. As a result, when the polymer is combined with a typical nonfullerene acceptor Y6, power conversion efficiencies of reaching 16% and VOC s of more than 0.84 V are observed, both of which are among the top values reported so far for "halogen-free" polymers. This study will serve as an important reference for designing π $\upi$ -conjugated polymers to achieve highly efficient and solution-processable OPVs.

A YAK1-type protein kinase, triacylglycerol accumulation regulator 1, in the green alga Chlamydomonas reinhardtii is a potential regulator of cell division and differentiation into gametes during photoautotrophic nitrogen deficiency.

Yet another kinase (YAK) 1 is a conserved eukaryotic protein kinase coordinating growth and development. We previously isolated a mutant of Chlamydomonas reinhardtii defective in the YAK1 ortholog triacylglycerol (TAG) accumulation regulator 1 (TAR1). The mutant tar1-1 displayed higher levels of chlorophyll, starch, TAG, and biomass than the parental strain C9 (renamed as C9-3) in photoautotrophic nitrogen (N)-deficient conditions. However, we found that the parental C9-3 showed faster chlorosis upon N-deficiency than the original C9 (C9-1) freshly recovered from cryopreservation, suggesting that C9-3 had acquired particular characteristics during long-term subculturing. To exclude phenotypes dependent on a particular parental strain, we newly created tar1 mutants from two wild-types, C9-1 and CC 125. Like tar1-1, the new tar1 mutants showed higher levels of chlorophyll and TAG/starch than the parental strain. Upon removal of N, Chlamydomonas cells divide once before ceasing further division. Previously, the single division after N-removal was arrested in tar1-1 in photomixotrophic conditions, but this phenotype was not observed in photoautotrophic conditions because of the particular characteristics of the parental C9-3. However, using C9- 1 and CC-125 as parental strains, we showed that cell division after N-removal was impaired in new tar1 mutants in photoautotrophic conditions. Consistent with the view that the division under N-deficiency is necessary for gametic differentiation, new tar1 mutants showed lower mating efficiency than the parental strains. Taken together, TAR1 was suggested to promote differentiation into gametes through the regulation of cell division in response to N-deficiency.

Effect of Water Adsorption Layers on the Friction Properties of Fluorinated Amorphous Carbon Films in Ambient Air.

Fluorinated amorphous carbon (a-C:F) films with different microstructures were prepared with bipolar-type plasma-based ion implantation and deposition method by changing the negative bias voltage, and the tribological properties were investigated in ambient air. Their surface chemistry and water adsorption properties were investigated to determine their friction properties. Microstructural analysis results showed that, as the negative bias voltage increased, the density of the films decreased with the promotion of graphitization. The water adsorption properties evaluated using a quartz crystal microbalance showed that a large adsorbed water weight was observed for the films deposited at high negative bias voltages. In contrast, these films exhibited thin water adsorption layers from the measurements with an ellipsometer. These results indicate that water molecules are adsorbed on the film surface and permeate into the films, particularly for the films deposited at high negative bias voltages. The friction properties in ambient air depend significantly on their microstructure and relative humidity (RH). Regardless of the RH, the higher the negative bias voltage during film deposition, the lower the friction coefficient. Since several water molecules existed on the surface of the film deposited with a low negative bias voltage, its surface was oxidized during sliding, which increased the friction coefficient. In addition, the friction coefficient of the films increased at high RH. The number of water molecules adsorbed on the film increased as the RH increased, causing a high shear force owing to many hydrogen bonds and/or high capillary force at the friction interface.

Mechanism of high D-aspartate production in the lactic acid bacterium Latilactobacillus sp. strain WDN19.

D-Aspartate (D-Asp) is a useful compound for a semisynthetic antibiotic and has potentially beneficial effects on humans. Several lactic acid bacteria (LAB) species produce D-Asp as a component of cell wall peptidoglycan. We previously isolated a LAB strain (named strain WDN19) that can extracellularly produce a large amount of D-Asp. Here, we show the factors that contribute to high D-Asp production ability. Strain WDN19 was most closely related to Latilactobacillus curvatus. The D-Asp production ability of strain WDN19 in a rich medium was 13.7-fold higher than that of L. curvatus DSM 20019. A major part of D-Asp was synthesized from L-Asp contained in the medium by aspartate racemase (RacD). During their cultivation, the RacD activity in strain WDN19 was higher than in strain DSM 20019, especially much higher in the early exponential growth phase because of the higher racD transcription and the higher activity of RacD itself of strain WDN19. In a synthetic medium, the extracellular production of D,L-Asp was observed in strain WDN19 but not in strain DSM 20019. The addition of L-asparagine (L-Asn) to the medium increased and gave D,L-Asp production in strains WDN19 and DSM 20019, respectively, suggesting L-Asp synthesis by L-asparaginase (AsnA). The L-Asn uptake ability of the strains was similar, but the AsnA activity in the middle exponential and early stationary growth phases and intracellular D,L-Asp was much higher in strain WDN19. In their genome sequences, only an aspartate aminotransferase gene was found among L-Asp-metabolizing enzymes, except for RacD, but was disrupted in strain WDN19 by transposon insertion. These observations indicated that the high D-Asp production ability of strain WDN19 was mainly based on high RacD and AnsA activities and L-Asp supply. KEY POINTS: • Strain WDN19 was suggested to be a strain of Latilactobacillus curvatus. • Extracellular high d-Asp production ability was not a common feature of L. curvatus. • High d-Asp production was due to high RacD and AnsA activities and l-Asp supply.

[A Case of Presacral Paraganglioma Resected by Laparoscopic Surgery].

A 25-year-old woman, with chief complaints of palpitation and vomiting, was suspected of having acute myocarditis and was taken to our critical care center. She was diagnosed with Takotsubo syndrome based on the results of echocardiography, coronary angiography, and myocardial biopsy. The 24-hour urine test showed high levels of normetanephrine and noradrenaline. The abdominal computed tomographic scan showed a presacral tumor (26 mm) just below the aortic bifurcation, and ¹³¹I-meta-iodobenzylguanidine scintigraphy showed abnormal accumulation in the tumor. Finally, she was diagnosed with Takotsubo syndrome associated with presacral paraganglioma. The hemodynamics became stable with conservative treatment. Then she underwent elective laparoscopic surgery. The histopathological analysis revealed paraganglioma. The immunohistochemistry for succinate dehydrogenase was negative in the tumor cells. There has been no recurrence as of 15 months after surgery.

Development of an enzymatic screening method for d-aspartate-producing lactic acid bacteria.

d-Aspartate (d-Asp) is an important intermediate for synthetic penicillin and an endogenous amino acid that plays important roles in the endocrine and nervous systems in animals including humans. Lactic acid bacteria (LABs) have been used as probiotics in humans, and some LAB species produce d-Asp as a component of cell wall peptidoglycan. LAB strains with greater d-Asp production would therefore be valuable for industrial d-Asp production. In this study, we developed an enzymatic screening method for d-Asp-producing LABs and isolated a strain with high d-Asp production. The d-Asp concentration in the culture medium was colorimetrically estimated up to 4 mM using d-aspartate oxidase (ChDDO) from the yeast Cryptococcus humicola strain UJ1 coupled with horseradish peroxidase, although a more accurate determination required correction because of interference by the medium component Mn2+. We isolated 628 LAB strains from various foods and screened them for d-Asp production using the enzymatic d-Asp assay method. The screening identified 13 d-Asp-producing LAB strains, which were suggested to belong to the genera Latilactobacillus, Levilactobacillus, Lactococcus, and Enterococcus. d-Asp production ability was likely to widely differ among the strains in the same genera and species. One strain, named strain WDN19, produced much higher d-Asp levels (1.84 mM), and it was closely related to Latilactobacillus curvatus. These results indicated that the enzymatic screening method was useful for identifying and isolating d-Asp-producing LABs rapidly and easily, and it might provide novel findings regarding d-Asp production by LABs.

Effect of Water Adsorption on the Frictional Properties of Hydrogenated Amorphous Carbon Films in Various Relative Humidities.

The tribological properties of hydrogenated amorphous carbon (a-C:H) films in ambient air were investigated from the microstructural point of view. a-C:H films with various microstructures (polymer-like, diamond-like, and graphite-like structures) were prepared, and the thickness of water adsorption layers on the films was measured. The adsorption behavior of water molecules on a-C:H films could be expressed with the Brunauer-Emmett-Teller (BET) isotherm, while the thicknesses of icelike and liquidlike water layers adsorbed on the films could be determined using the BET parameters C and nma. The polymer-like films exhibited the thickest icelike and liquidlike water adsorption layers, which decreased as the film structure changed to a diamond-like or a graphite-like structure. A strong relationship was observed between the thickness of water adsorption layers and the surface oxidation of the a-C:H films. The friction coefficient of the films in ambient air can be well explained by the surface oxidation and the thickness of water adsorption layers. Polymer-like films showed high friction coefficients due to the formation of a thick water layer on the films originated from the high surface oxidation of the film surface, whereas the graphite-like film exhibited a low friction coefficient due to low oxidation and a thin water adsorption layer. Furthermore, friction tests between the a-C:H films with different microstructures under ambient air were performed to determine the lowest friction pair in various relative humidities (RHs).

[A Case of Metachronous Bilateral Epididymal Tuberculosis after BCG Instillation Therapy].

Beginning in May 2016, an 83-year-old male underwent three transurethral resections for recurrent bladder cancer. In June 2017, following a positive urine cytology exam, a random biopsy of the bladder was performed. The histopathological findings revealed urothelial carcinoma, high grade, pTis. Treatment consisted of bacillus Calmette-Guerin (BCG) instillation. In February 2018, he complained of left scrotal swelling and pain ; and, was diagnosed with left epididymitis. However, based on resistance to the antibiotic agent, epididymal tuberculosis after BCG therapy was suspected and resection of the left testis and epididymis was performed. Histopathological findings revealed epididymal tuberculosis. Three months after the left orchiectomy, the patient complained of right scrotal swelling and pain. Based on antibiotic resistance and the positive findings of a urinary mycobacterium tuberculosis polymerase chain reaction assay, metachronous right epididymal tuberculosis was suspected and the patient underwent resection of the right epididymis. While the histopathological findings did not indicate tuberculosis, the urinary mycobacterium culture was positive. The patient was diagnosed with right epididymal tuberculosis and after surgery was administered an antituberculosis drug.

Excited-State Dynamics and Thermally Activated Delayed Fluorescence in the Classic Electron Acceptor Tetracyanoquinodimethane.

Tetracyanoquinodimethane (TCNQ) is identified as one of the most important and classic constituents for the synthesis of organic conductors and shows an acute response of the fluorescence quantum yield to subtle changes in the polarity of solvents. Here, we report on characterization of the excited-state dynamics of TCNQ using time-resolved fluorescence and femtosecond transient absorption (TA) measurements in various solvents. Fluorescence decay and TA dynamics reveal that the fluorescence emissive and nonemissive states reach equilibrium within the fluorescence lifetime in carbon tetrachloride. Thermally activated delayed fluorescence of TCNQ is also revealed. The fluorescence in the polar solvents is quenched by the forward relaxation to the nonemissive state within a few picoseconds and the subsequent rapid de-excitation of the nonemissive state within a few tens of picoseconds. The nonemissive state is probably assigned to the triplet state, and the change in the forward and reverse intersystem crossing rates can be responsible for the response of the fluorescence to the polarity of solvents.

Photophysics and Inverted Solvatochromism of 7,7,8,8-Tetracyanoquinodimethane (TCNQ).

We report absorption, fluorescence, and Raman spectroscopy of 7,7,8,8-tetracyanoquinodimethane (TCNQ) in a variety of solvents. The fluorescence quantum yields (QYs) of linear alkane solutions are similar to one another, but QY is shown to acutely decrease in other solvents with increasing polarities. The slope of the solvatochromic plot of absorption maxima is inverted from negative to positive with an increase in solvent polarity. A significant change in the frequency of carbon-carbon double bond stretching modes is not observed in Raman spectra of TCNQ in different solvents. The molar absorption coefficient is determined to calculate the oscillator strength of the absorption band. The radiative decay rate constant calculated from the oscillator strength is approximately ten times larger than that elucidated from the fluorescence lifetime and QY. These spectroscopic parameters reveal that the relaxation occurs from a Franck-Condon excited state to a distinct fluorescence emissive state with a smaller transition dipole moment.

Aortic valve aneurysm associated with infective endocarditis: case report and review of literature.

Although there are several mitral valve aneurysm reports, studies on aortic valve aneurysm are extremely rare. This paper describes an uncommon case of a large saccular aortic valve aneurysm associated with infective endocarditis. A 37-year-old man was hospitalized in our hospital with fever and dyspnea. Echocardiography found severe aortic regurgitation and aortic valve aneurysm of the non-coronary cusp going in and out of the left ventricular chamber. Blood cultures grew Streptococcus viridance. Therefore, the patient underwent aortic valve replacement. During the operation, we observed a 30 × 20 mm ruptured aneurysm that arose from the non-coronary cusp. The aortic valve containing the aneurysm was resected and replaced with a mechanical heart valve. Histopathological examination of the aortic valve aneurysm showed active inflammatory changes. Infective endocarditis was considered to be the cause of this aortic valve aneurysm.

Support system for pathologists and researchers.

AIMS: In Japan, cancer is the most prevalent cause of death; the number of patients suffering from cancer is increasing. Hence, there is an increased burden on pathologists to make diagnoses. To reduce pathologists' burden, researchers have developed methods of auto-pathological diagnosis. However, virtual slides, which are created when glass slides are digitally scanned, saved in a unique format, and it is difficult for researchers to work on the virtual slides for developing their own image processing method. This paper presents the support system for pathologists and researchers who use auto-pathological diagnosis (P-SSD). Main purpose of P-SSD was to support both of pathologists and researchers. P-SSD consists of several sub-functions that make it easy not only for pathologists to screen pathological images, double-check their diagnoses, and reduce unimportant image data but also for researchers to develop and apply their original image-processing techniques to pathological images. METHODS: We originally developed P-SSD to support both pathologists and researchers developing auto-pathological diagnoses systems. Current version of P-SSD consists of five main functions as follows: (i) Loading virtual slides, (ii) making a supervised database, (iii) learning image features, (iv) detecting cancerous areas, (v) displaying results of detection. RESULTS: P-SSD reduces computer memory size random access memory utilization and the processing time required to divide the virtual slides into the smaller-size images compared with other similar software. The maximum observed reduction in computer memory size and reduction in processing time is 97% and 99.94%, respectively. CONCLUSIONS: Unlike other vendor-developed software, P-SSD has interoperability and is capable of handling virtual slides in several formats. Therefore, P-SSD can support both of pathologists and researchers, and has many potential applications in both pathological diagnosis and research area.

Both movement-end and task-end are critical for error feedback in visuomotor adaptation: a behavioral experiment.

An important issue in motor learning/adaptation research is how the brain accepts the error information necessary for maintaining and improving task performance in a changing environment. The present study focuses on the effect of timing of error feedback. Previous research has demonstrated that adaptation to displacement of the visual field by prisms in a manual reaching task is significantly slowed by delayed visual feedback of the endpoint, suggesting that error feedback is most effective when given at the end of a movement. To further elucidate the brain mechanism by which error information is accepted in visuomotor adaptation, we tested whether error acceptance is linked to the end of a given task or to the end of an executed movement. We conducted a behavioral experiment using a virtual shooting task in which subjects controlled their wrist movements to meet a target with a cursor as accurately as possible. We manipulated the timing of visual feedback of the impact position so that it occurred either ahead of or behind the true time of impact. In another condition, the impact timing was explicitly indicated by an additional cue. The magnitude of the aftereffect significantly varied depending on the timing of feedback (p < 0.05, Friedman's Test). Interestingly, two distinct peaks of aftereffect were observed around movement-end and around task-end, irrespective of the existence of the timing cue. However, the peak around task-end was sharper when the timing cue was given. Our results demonstrate that the brain efficiently accepts error information at both movement-end and task-end, suggesting that two different learning mechanisms may underlie visuomotor transformation.

[Papillary fibroelastoma of the left ventricular outflow tract].

Cardiac papillary fibroelastoma is an uncommon tumor, and especially the one located in the left ventricular outflow tract wall is rare. The patient is a 69-year-old female. Multi-detector-row computed tomography (MDCT) revealed a 20×15 mm tumor attached to the left ventricular outflow tract wall under the left coronary cusp. The tumor was surgically removed with a slight margin. The tumor was milk-white in color, and had an egg-like appearance. The histological findings revealed papillary fibroelastoma. The postoperative course was uneventful.

Ruptured bronchial artery aneurysm associated with bronchiectasis: a case report.

A massive hemothorax from a ruptured bronchial artery aneurysm (BAA) is very rare. Only 12 cases of ruptured mediastinal BAA have been reported. This case study describes a 77-year-old female with bronchiectasis who presented with anemia, hypertension, hemothorax, and a mediastinal mass. A chest tube was inserted through which 2 liters of unclotted blood was drained from the left pleural cavity. An enhanced computed tomography scan revealed a ruptured 3-cm diameter mediastinal aneurysm of a bronchial artery supplying the left lower lobe. Transcatheter artery embolization (TAE) with multiple microcoils was performed successfully. Although the patient needed a transfusion, the subsequent course was uneventful. In the absence of trauma or other causes for hemothorax and mediastinal hemorrhage, the possibility of a BAA should be considered. TAE is the treatment method of choice as a minimally invasive strategy in patients with ruptured BAA.

Optimal method of coronary endarterectomy for diffusely diseased coronary arteries.

BACKGROUND: Although several techniques for coronary artery bypass grafting have been introduced that incorporate coronary endarterectomy (CE), there is little information about late patency among the various CE methods. To clarify the quality of CE, we assessed clinical and angiographic results of our experience with this procedure on 127 patients who had diffusely diseased coronary arteries. METHODS: Between January 1994 and December 2002, 127 patients underwent coronary artery bypass grafting with CE. Sixty-eight patients undergoing CE with long arteriotomies and on-lay patch bypass grafting (group O) were compared with 59 patients undergoing CE with the conventional pull-out method (group P). RESULTS: Thirty-day mortality was 2.9% in group O and 6.8% in group P. The early angiographic results of 115 patients revealed a patency rate of 92.1% (grade A: 79.4%) in group O and 88.6% (grade A: 68.6%) in group P. Actuarial survival at 5 years was 90.7% in group O and 74.0% in group P (p = 0.1). Angiograms performed on 78 patients after a mean period of 21 +/- 16 months showed a patency rate of 89.1% (grade A:76.1%) in group O and 81.0% (grade A: 38.1%) in group P (grade A: p < 0.001). CONCLUSIONS: The midterm angiographic results of CE with long arteriotomies and on-lay patch bypass grafting were better than the results obtained with the conventional pull-out method. This procedure was found to be safe and effective for complete revascularization in patients with a severely and diffusely diseased coronary artery.

Persistent left superior vena cava draining to left atrium with normal coronary sinus.

In embryology, a persistent connection of the left superior vena cava to the left atrium rarely coexists with a coronary sinus. We herein report an unusual case of persistent left superior vena cava terminating in a left atrium with normal coronary sinus, which was revealed at the time of permanent pacemaker implantation after a second operation for recurrent left atrioventricular valve regurgitation. Because this anomaly had gone undiagnosed at the first operation, we were unable to diagnose it prior to the second operation, because the preoperative coronary angiogram clearly demonstrated a coronary sinus that was not dilated. We would have repaired the anomaly using a patch or other procedure had it been diagnosed before the second operation in order to prevent cyanosis or brain complications secondary to right-to-left shunting. One should always be on guard for this rare condition.

Pseudoaneurysm of the dorsalis pedis artery causing neurological deficit.

Pseudoaneurysm of the dorsalis pedis artery is very rare. This case report describes a 71-year-old man with an idiopathic aneurysm of the dorsalis pedis artery that caused neurological deficit. Surgical resection was performed and his symptoms improved.

Extensive thoracoabdominal aortic aneurysm repair using deep hypothermic bypass and circulatory arrest.

We sought to evaluate the safety and usefulness of deep hypothermic cardiopulmonary bypass with intervals of circulatory arrest for extensive thoracoabdominal aortic aneurysms. Between March 1994 and December 2002, 17 patients with Crawford type I and II were reviewed retrospectively. The patients were divided into two groups: group H (hypothermic circulatory arrest, n = 8) and group N (normothermic cardiopulmonary bypass, n = 9). In group H, in-hospital mortality was 12.5%, and that in group N was 11.1%. Operation times were similar between the two groups though the cardiopulmonary bypass time was significantly shorter in group N than in group H (p < 0.05). Postoperative paraplegia occurred in 1 patient of group N. Postoperative renal dysfunction occurred in none of group H except in 1 preoperative dialysis case, whilst it occurred in 6 patients of group N. Postoperative creatinine levels were significantly higher in group N than in group H. Three cases in group H required tracheostomy. Our experience with hypothermic cardiopulmonary bypass and circulatory arrest for diffuse type thoracoabdominal aortic aneurysm confirms the safety and efficacy of this technique. Although respiratory complications remain a problem, the technique is considered to be effective for renal protection.

Complete revascularization in patients with severe left ventricular dysfunction.

OBJECTIVE: This study evaluates whether patients with coronary artery disease and severely depressed left ventricular ejection fraction (LVEF) benefit from complete revascularization by multivessel coronary artery bypass. METHODS: From April 1994 to May 2002, 42 patients who underwent coronary artery bypass grafting (CABG) at our institution had impaired left ventricular (LV) function [an ejection fraction (EF) of 30% or less]. The average preoperative LVEF was 23.8%. The mean number of grafts was 4.6. Complete revascularization by multivessel bypass grafting was the goal for all patients. RESULTS: Thirty days mortality was 0 and hospital mortality was 2.4%. The mean graft patency rate for 35 (83%) patients at one month was 98.8%. The mean postoperative LVEF improved significantly, from 23.8% to 35.2% (p<0.05), and the New York Heart Association (NYHA) classification was improved in most patients. The Kaplan-Meier estimate of survival at 5 years was 83.1%, and that of the cardiac event-free rate at 5 years was 77.5%. CONCLUSION: For patients with poor LV function, complete surgical revascularization by multivessel bypass grafting can be performed safely, with satisfactory hospital mortality and long-term results.