A Dibenzo[g,p]chrysene-Based Organic Semiconductor with Small Exciton Binding Energy via Molecular Aggregation.

Exciton binding energy (Eb) is understood as the energy required to dissociate an exciton in free-charge carriers, and is known to be an important parameter in determining the performance of organic opto-electronic devices. However, the development of a molecular design to achieve a small level of Eb in the solid state continues to lag behind. Here, to investigate the relationship between aggregation and Eb, star-shaped π-conjugated compounds DBC-RD and TPE-RD were developed using dibenzo[g,p]chrysene (DBC) and tetraphenylethylene (TPE). Theoretical calculations and physical measurements in solution showed no apparent differences between DBC-RD and TPE-RD, indicating that these molecules possess similar properties on a single-molecule level.  By contrast, pristine films incorporating these molecules showed significantly different levels of electron affinity, ionization potential, and optical gap. Also, DBC-RD had a smaller Eb value of 0.24 eV compared with that of TPE-RD (0.42 eV). However, these molecules showed similar Eb values under dispersed conditions, which suggested that the decreased Eb of DBC-RD in pristine film is induced by molecular aggregation. By comparison with TPE-RD, DBC-RD showed superior performances in single-component organic solar cells and organic photocatalysts. These results indicate that a molecular design suitable for aggregation is important to decrease the Eb in films.

Large-scale citizen science reveals predictors of sensorimotor adaptation.

Sensorimotor adaptation is essential for keeping our movements well calibrated in response to changes in the body and environment. For over a century, researchers have studied sensorimotor adaptation in laboratory settings that typically involve small sample sizes. While this approach has proved useful for characterizing different learning processes, laboratory studies are not well suited for exploring the myriad of factors that may modulate human performance. Here, using a citizen science website, we collected over 2,000 sessions of data on a visuomotor rotation task. This unique dataset has allowed us to replicate, reconcile and challenge classic findings in the learning and memory literature, as well as discover unappreciated demographic constraints associated with implicit and explicit processes that support sensorimotor adaptation. More generally, this study exemplifies how a large-scale exploratory approach can complement traditional hypothesis-driven laboratory research in advancing sensorimotor neuroscience.

Correction to "Performance Improvement with an Ultrathin p-Type Interfacial Layer in n-Type Vertical Organic Field-Effect Transistors Based on Reduced Graphene Oxide Electrode".

[This corrects the article DOI: 10.1021/acsomega.2c02085.].

Progression of albuminuria and podocyte injury in focal segmental glomerulosclerosis inhibited by enhanced glycosphingolipid GM3 via valproic acid.

Focal segmental glomerulosclerosis, characterized by decreased numbers of podocytes in glomeruli, is a common cause of refractory nephrotic syndrome. Recently, we showed that enhanced glycosphingolipid GM3 expression after administration of valproic acid, an upregulator of ST3GAL5/St3gal5, was effective in preventing albuminuria and podocyte injury. We also revealed the molecular mechanism for this preventive effect, which involves GM3 directly binding nephrin that then act together in glycolipid-enriched membrane (GEM) fractions under normal conditions and in non-GEM fractions under nephrin injury conditions. Kidney disease is frequently referred to as a "silent killer" because it is often difficult to detect subjective symptoms. Thus, primary treatment for these diseases is initiated after the onset of disease progression. Consequently, the efficacy of enhanced levels of GM3 induced by valproic acid needs to be evaluated after the onset of the disease with severe albuminuria such as focal segmental glomerulosclerosis. Here, we report the therapeutic effect of enhanced GM3 expression induced via administration of valproic acid on albuminuria and podocyte injury after the onset focal segmental glomerulosclerosis in anti-nephrin antibody treated mice. Our findings suggest elevated levels of GM3 following treatment with valproic acid has therapeutic utility for kidney disease associated with severe albuminuria and podocyte injury.

Synthesis and Characterization of Dibenzothieno[a,f]pentalenes Enabling Large Antiaromaticity and Moderate Open-Shell Character through a Small Energy Barrier for Bond-Shift Valence Tautomerization.

Experimental and theoretical rationalization of bond-shift valence tautomerization, characterized by double-well potential surfaces, is one of the most challenging topics of study among the rich electronic properties of antiaromatic molecules. Although the pseudo-Jahn-Teller effect (PJTE) is an essential effect to provide attractive characteristics of 4nπ systems, an understanding of the structure-property relationship derived from the PJTE for planar 4nπ electron systems is still in its infancy. Herein, we describe the synthesis and characterization of two regioisomers of the thiophene-fused diareno[a,f]pentalenes 6 and 7. The magnetic and optoelectronic properties characterize these sulfur-doped diareno[a,f]pentalenes as open-shell antiaromatic molecules, in sharp contrast to the closed-shell antiaromatic systems of 3 and 5, in which these main cores consist of the same number of π electrons as 6 and 7. Notably, thiophene-fused 6b and 7b showed pronounced antiaromaticity, the strongest among the previous systems, as well as moderate open-shell characteristics. Our experimental and theoretical investigations concluded that these properties of 6b and 7b are derived from the small energy barrier Ea‡ for the bond-shift valence tautomerization. The energy profile of the single crystal of 6b showed the temperature-dependent structural variations assigned to the dynamic mutual exchange between the two Cs-symmetric structures, which was also supported by changes in the chemical shifts of variable-temperature 1H NMR spectra in the solution phase. Both experimental and computational results revealed the importance of introducing heteroaromatic rings into 4nπ systems for controlling the PJTE and manifesting the antiaromatic and open-shell natures originating from the high-symmetric structure. The findings of this study advance the understanding of antiaromaticity characterized by the PJTE by controlling the energy barrier for bond-shift valence tautomerizations, potentially leading to the rational design of optoelectronic devices based on novel antiaromatic molecules possessing the strong contributions of their high-symmetric geometries.

Radial bias alters high-level motion perception.

The visual system involves various orientation and visual field anisotropies, one of which is a preference for radial orientations and motion directions. By radial, we mean those directions coursing symmetrically outward from the fovea into the periphery. This bias stems from anatomical and physiological substrates in the early visual system. We recently reported that this low-level visual anisotropy can alter perceived object orientation. Here, we report that radial bias can also alter another higher-level system, the perceived direction of apparent motion. We presented a bistable apparent motion quartet in the center of the screen while participants fixated on various locations around the quartet. Participants (N = 22) were strongly biased to see the motion direction that was radial with respect to their fixation, controlling for any biases with center fixation. This was observed using a vertical-horizontal quartet as well as an oblique quartet (45° rotated quartet). The latter allowed us to rule out the contribution of the hemisphere effect where motion across the midline is perceived less often. These results extend our earlier findings on perceived object orientation, showing that low-level structural aspects of the visual system alter yet another higher-level visual process, that of apparent motion perception.

Possibilities and Limitations in Monomer Combinations for Ternary Two-Dimensional Covalent Organic Frameworks.

The diversity and complexity of covalent organic frameworks (COFs) can be largely increased by incorporating multiple types of monomers with different topologies or sizes. However, an increase in the number of monomer types significantly complicates the COF formation process. Accordingly, much remains unclear regarding the viability of monomer combinations for ternary or higher-arity COFs. Herein, we show that, through an extensive examination of 12 two-nodes-one-linker ([2 + 1]) combinations, monomer-set viability is determined primarily by the conformational strain originating from disordered monomer arrangements, rather than other factors such as the difference in COF formation kinetics between monomers. When monomers cannot accommodate the strain associated with the formation of a locally disordered, yet crystalline framework, the corresponding [2 + 1] condensation yields a mixture of different COFs or an amorphous polymer. We also demonstrate that a node-linker pair that does not form a binary COF can be integrated to generate a single-phase framework upon addition of a small amount of the third component. These results will clarify the factors behind the successful formation of multicomponent COFs and refine their design by enabling accurate differentiation between allowed and disallowed monomer combinations.

Rethinking Vision and Action.

Action is an important arbitrator as to whether an individual or a species will survive. Yet, action has not been well integrated into the study of psychology. Action or motor behavior is a field apart. This is traditional science with its need for specialization. The sequence in a typical laboratory experiment of see → decide → act provides the rationale for broad disciplinary categorizations. With renewed interest in action itself, surprising and exciting anomalous findings at odds with this simplified caricature have emerged. They reveal a much more intimate coupling of vision and action, which we describe. In turn, this prompts us to identify and dwell on three pertinent theories deserving of greater notice.

Gut dysbiosis and bacterial translocation in the aneurysmal wall and blood in patients with abdominal aortic aneurysm.

Inflammation plays a part in the development of abdominal aortic aneurysm (AAA), and the gut microbiota affects host inflammation by bacterial translocation. The relationship between abdominal aortic aneurysm and the gut microbiota remains unknown. This study aimed to detect bacterial translocation in the aneurysmal wall and blood of patients with abdominal aortic aneurysm, and to investigate the effect of the gut microbiota on abdominal aortic aneurysm. We investigated 30 patients with abdominal aortic aneurysm from 2017 to 2019. We analysed the aneurysmal wall and blood using highly sensitive reverse transcription-quantitative polymerase chain reaction, and the gut microbiota was investigated using next-generation sequencing. In the 30 patients, bacteria were detected by reverse transcription- quantitative polymerase chain reaction in 19 blood samples (detection rate, 63%) and in 11 aneurysmal wall samples (detection rate, 37%). In the gut microbiota analysis, the Firmicutes/Bacteroidetes ratio was increased. The neutrophil-lymphocyte ratio was higher (2.94 ± 1.77 vs 1.96 ± 0.61, P < 0.05) and the lymphocyte-monocyte ratio was lower (4.02 ± 1.25 vs 5.86 ± 1.38, P < 0.01) in the bacterial carrier group than in the bacterial non-carrier group in blood samples. The volume of intraluminal thrombus was significantly higher in the bacterial carrier group than in the bacterial non-carrier group in aneurysmal wall samples (64.0% vs 34.7%, P < 0.05). We confirmed gut dysbiosis and bacterial translocation to the blood and aneurysmal wall in patients with abdominal aortic aneurysm. There appears to be a relationship between the gut microbiota and abdominal aortic aneurysm.

Radial Bias Alters Perceived Object Orientation.

Orientation sensitivity is a fundamental property of the visual system, but not all orientations are created equal. For instance, radially oriented stimuli, aligned with a line intersecting the center of gaze, produce greater activity throughout the visual cortex and are associated with greater perceptual sensitivity compared with other orientations. Here, we discuss a robust visual illusion that is likely related to this preference. Using a continuous response measure, participants (N = 36 adults) indicated the gap position in a peripheral Landolt C placed in one of eight orientations and eight locations along four meridians (vertical, horizontal, 45°, 135°). The error distributions revealed that the perceived gap was attracted toward the radial axis. For instance, the gap in a regular C would often be wrongly perceived as tilted 45° corresponding to the oblique meridian where it was placed. These findings demonstrate an unsuspected early-vision influence on the perceived orientation of an object.

Glycosphingolipid GM3 prevents albuminuria and podocytopathy induced by anti-nephrin antibody.

Podocytopathy, which is characterized by injury to podocytes, frequently causes proteinuria or nephrotic syndrome. There is currently a paucity of effective therapeutic drugs to treat proteinuric kidney disease. Recent research suggests the possibility that glycosphingolipid GM3 maintains podocyte function by acting on various molecules including nephrin, but its mechanism of action remains unknown. Here, various analyses were performed to examine the potential relationship between GM3 and nephrin, and the function of GM3 in podocytes using podocytopathy mice, GM3 synthase gene knockout mice, and nephrin injury cells. Reduced amounts of GM3 and nephrin were observed in podocytopathy mice. Intriguingly, this reduction of GM3 and nephrin, as well as albuminuria, were inhibited by administration of valproic acid. However, when the same experiment was performed using GM3 synthase gene knockout mice, valproic acid administration did not inhibit albuminuria. Equivalent results were obtained in model cells. These findings indicate that GM3 acts with nephrin in a collaborative manner in the cell membrane. Taken together, elevated levels of GM3 stabilize nephrin, which is a key molecule of the slit diaphragm, by enhancing the environment of the cell membrane and preventing albuminuria. This study provides novel insight into new drug discovery, which may offer a new therapy for kidney disease with albuminuria.

Delayed fluorescence from inverted singlet and triplet excited states.

Hund's multiplicity rule states that a higher spin state has a lower energy for a given electronic configuration1. Rephrasing this rule for molecular excited states predicts a positive energy gap between spin-singlet and spin-triplet excited states, as has been consistent with numerous experimental observations over almost a century. Here we report a fluorescent molecule that disobeys Hund's rule and has a negative singlet-triplet energy gap of -11 ± 2 meV. The energy inversion of the singlet and triplet excited states results in delayed fluorescence with short time constants of 0.2 µs, which anomalously decrease with decreasing temperature owing to the emissive singlet character of the lowest-energy excited state. Organic light-emitting diodes (OLEDs) using this molecule exhibited a fast transient electroluminescence decay with a peak external quantum efficiency of 17%, demonstrating its potential implications for optoelectronic devices, including displays, lighting and lasers.

Performance Improvement with an Ultrathin p-Type Interfacial Layer in n-Type Vertical Organic Field-Effect Transistors Based on Reduced Graphene Oxide Electrode.

Vertical organic field-effect transistors (VOFETs) with a large current on/off ratio and easy fabrication process are highly desirable for future organic electronics. In this paper, we proposed an ultrathin p-type copper (II) phthalocyanine (CuPc) interfacial layer in reduced graphene oxide (rGO)-based VOFETs. The CuPc interfacial layer was sandwiched between the rGO electrode and the N,N'-dioctyl-3,4,9,10-perylenedicarboximide (PTCDI-C8) organic layer. The introduced CuPc interfacial layer not only decreased the off-current density of the device but also slightly enhanced the on-current density. The threshold voltage of the device was also effectively improved and stabilized at around 0 V. The obtained device exhibited a current on/off ratio exceeding 106, which is the largest value reported for rGO-based VOFETs. The vertical electron mobility of the PTCDI-C8 layer estimated by the space-charge-limited current technique was 1.14 × 10-3 cm2/(V s). However, it was not the main limiting factor for the current density in this device. We totally fabricated 48 devices, and more than 75% could work. Besides, the device was stable with little performance degradation after 1 month. The use of low-cost, solution-processable rGO as work-function-tunable electrode and the application of an ultrathin CuPc interfacial layer in VOFETs may open up opportunities for future organic electronics.

A systematic review of management of ureteroarterial fistula.

OBJECTIVE: Ureteroarterial fistula (UAF) is lethal condition. However, no consensus has been reached regarding the diagnosis and treatment of UAF owing to its rarity. The aim of our report was to present an actual case of UAF and systematically review the symptoms, risk factors, diagnosis, and treatment of this condition. METHODS: The case study was of a 52-year-old woman who had experienced a massive hemorrhage during urinary stent replacement. For the systematic review of studies of UAF, those written in English and reported from 1939 to 2020 were searched for on PubMed using the keywords "uretero-arterial fistula," "arterio-ureteral fistula," and "hematuria." RESULTS: We included 121 studies with 235 patients (mean age, 66.0 years; 139 women [59.1%]) in our review. UAF had occurred most frequently in the common iliac artery (n = 112; 47.7%). Almost all patients (n = 232; 98.7%) had complained of hematuria. The risk factors for UAF were pelvic surgery (n = 205; 87.2%), the long-term use of urinary stents (n = 170; 72.3%), oncologic radiotherapy (n = 107; 45.5%), and malignancy (n = 159; 67.7%). Although computed tomography can detect various useful findings such as extravasation, pseudoaneurysm, hydronephrosis, and opacification of ureters, it was diagnostically useful for only one third of the cases. Angiography was useful for the diagnoses of UAF for 124 (66.3%) of the 187 patients (79.6%) who had undergone angiography. With regard to treatment, endovascular approaches have been widely used in recent years because their invasiveness is lesser than that of open surgical repair. In the era of endovascular therapy, the indications for open surgical repair include ureteral-intestinal fistula, abscess formation, and graft infection after endovascular therapy. CONCLUSIONS: Computed tomography can be recommended as the first examination for patients with risk factors for UAF because of its usefulness. Subsequently, angiography should be considered because UAF can be treated using an endovascular approach after diagnostic angiography. The diagnosis and treatment of UAF can often be difficult; therefore, the important first step of diagnosis is suspecting the occurrence of UAF and using a multidisciplinary approach.

Analysis of prognostic factors for postoperative complications and reinterventions after open surgical repair and endovascular aneurysm repair in patients with abdominal aortic aneurysm.

OBJECTIVE: A definitive treatment for patients with abdominal aortic aneurysm considering age and comorbidities has not been identified. In the present study, we retrospectively validated treatment outcomes in Japanese patients and proposed the treatment strategy of open surgical repair (OSR) and endovascular aneurysm repair (EVAR). METHODS: We retrospectively analyzed data for patients undergoing EVAR or OSR between 2006 and 2017. Patients with ruptured abdominal aortic aneurysm were excluded. We examined post-operative complications, operative mortality, re-intervention and prognosis. RESULTS: Throughout the study period, 405 patients underwent EVAR and 176 patients underwent OSR. The percentage of patients with post-operative complications was 35.8% in the OSR group, compared with 13.1% in the EVAR group (P < 0.01). The operative mortality rate was 0.49% in the EVAR group and 0.57% in the OSR group (P = 1.00). With a multivariate analysis, age, hemodialysis, modified Frailty Index (mFI), and OSR were risk factors for post-operative complications. The 5-year re-intervention free survival rate was 63.0 % with hostile neck EVAR compared with 83.1 % with favorable neck EVAR and 86.1 % with OSR group (P < 0.01). With a multivariate analysis, hemodialysis, mFI, and hostile neck EVAR were risk factors for re-intervention. The 5-year overall survival rate was 51.9 % with hostile neck EVAR compared with 73.2 % with favorable neck EVAR and 79.0 % with OSR group (P < 0.01). With a multivariate analysis, age, mFI, and hostile neck EVAR were poor prognostic factors. CONCLUSION: Age, mFI, hemodialysis and hostile neck anatomy are useful predictors of post-operative complications, re-intervention and overall survival, and could be useful for informing treatment selection between OSR and EVAR.

Coming of Age in Science: Just Look?

With Professor Patrick Cavanagh, I started the Harvard Vision Sciences Laboratory in 1990. Blessed with the largesse of a wealthy university, we occupied a very large common space. Here, students pursued their own projects in a uniquely cooperative and exciting scientific environment. The times were just right in the emerging and expanding field of vision science. With good thesis projects under their belt, most of the students went on to successful careers. However, my own coming of age in science did not have such a promising start. It only started well into my thirties when I joined the Smith Kettlewell Eye Research Institute in San Francisco. Providentially, it was there that I had the rare and unique opportunity to work closely and essentially only with peers (not students). Through these intense collaborations, I found my way as a scientist. Most of this account describes these formative years.

The ability to predict actions of others from distributed cues is still developing in 6- to 8-year-old children.

Adults use distributed cues in the bodies of others to predict and counter their actions. To investigate the development of this ability, we had adults and 6- to 8-year-old children play a competitive game with a confederate who reached toward one of two targets. Child and adult participants, who sat across from the confederate, attempted to beat the confederate to the target by touching it before the confederate did. Adults used cues distributed through the head, shoulders, torso, and arms to predict the reaching actions. Children, in contrast, used cues in the arms and torso, but we did not find any evidence that they could use cues in the head or shoulders to predict the actions. These results provide evidence for a change in the ability to respond rapidly to predictive cues to others' actions from childhood to adulthood. Despite humans' sensitivity to action goals even in infancy, the ability to read cues from the body for action prediction in rapid interactive settings is still developing in children as old as 6 to 8 years of age.

Single-Component Organic Solar Cells Based on Intramolecular Charge Transfer Photoabsorption.

Conjugated donor-acceptor molecules with intramolecular charge transfer absorption are employed for single-component organic solar cells. Among the five types of donor-acceptor molecules, the strong push-pull structure of DTDCPB resulted in solar cells with high JSC, an internal quantum efficiency exceeding 20%, and high VOC exceeding 1 V with little photon energy loss around 0.7 eV. The exciton binding energy (EBE), which is a key factor in enhancing the photocurrent in the single-component device, was determined by quantum chemical calculation. The relationship between the photoexcited state and the device performance suggests that the strong internal charge transfer is effective for reducing the EBE. Furthermore, molecular packing in the film is shown to influence photogeneration in the film bulk.

Synthesis, Structure, and Chiroptical Properties of Indolo- and Pyridopyrrolo-Carbazole-Based C2 -Symmetric Azahelicenes.

Treatment of 11,12-bis(1,1'-biphenyl-3-yl or 6-phenylpyridin-2-yl)-substituted 11,12-dihydro-indolo[2,3-a]carbazole with an oxidizing system of Pd(II)/Ag(I) induced effective double dehydrogenative cyclization to afford the corresponding π-extended azahelicenes. The optical resolutions were readily achieved by a preparative chiral HPLC. It was found that the pyridopyrrolo-carbazole-based azahelicene that contains four nitrogen atoms exhibits ca. 6 times larger dissymmetry factors both in circularly dichroism (CD) and circularly polarized luminescence (CPL), |gCD | and |gCPL | values being 1.1×10-2 and 4.4×10-3 , respectively, as compared with the parent indolocarbazole-based azahelicene. Theoretical calculations at the RI-CC2 level were employed to rationalize the observed enhanced chiroptical responses. The (chir)optical properties of the former helicene was further tuned by a protonation leading to remarkable red-shift with a considerable enhancement of the |gCPL | value.

Platelet Count Recovery after Endovascular Aneurysm Repair for Abdominal Aortic Aneurysm.

Objective: To find a new predictor of endoleak (EL) and aneurysm sac expansion after endovascular aneurysm repair (EVAR), we evaluated the platelet count recovery (PCR) process after EVAR. Materials and Methods: Two hundred five patients treated with elective EVAR from 2007 to 2015 were retrospectively analyzed. We compared the platelet count ratio until postoperative day (POD) 7 to the presurgical baseline between patients with and without persistent EL (≥ 6 months). Subsequently, we calculated the optimal platelet count ratio for distinguishing persistent EL using receiver-operating characteristics analysis. A platelet count ratio on POD7 ≥118% was defined as the PCR. We evaluated the PCR's influence on the cumulative aneurysm sac expansion rate. Results: The average platelet count ratio on POD7 rose above baseline (112%), and the ratio was attenuated by persistent EL (103%). Of 205 patients, 126 (61%) were assigned to the disturbed PCR group (PCR(-) group). Cumulative aneurysm sac expansion rate was higher in the PCR(-) group than the PCR(+) group (34.4% vs. 12.8% in 5 years, p=0.01). Conclusion: Disturbed PCR after EVAR may be associated with ELs and eventual aneurysm sac expansion.