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To evaluate the outer retinal microstructure and visual function after idiopathic macular hole (MH) surgery using internal limiting membrane (ILM) peeling with and without Brilliant Blue G (BBG) staining.Retrospective, consecutive case series.A total of 49 eyes of 47 patients were enrolled: 23 eyes of 23 patients with MH who underwent ILM peeling without dyes (control group) and 26 eyes of 26 patients who underwent BBG staining (BBG group). The lengths of defects of the photoreceptor ellipsoid zone (EZ), external limiting membrane (ELM), and interdigitation zone (IZ) were measured.The rate of MH closure after initial surgery was 95.6% (22/23 eyes) for the control group versus 100% (26/26 eyes) for the BBG group. In the 48 eyes with MH closure, the recovery rate of ELM deficiency and change in IZ deficiency showed no difference between the groups. The changes in EZ deficiency at 1 and 12 months were greater in the BBG group than in the control group. (P = 0.047 and 0.031). Visual acuity was better in the BBG group than in the control group during 12 months postoperatively (P 0.001-0.038).Eyes undergoing BBG-assisted MH surgery achieved faster recovery of the outer retinal structures and greater visual improvement than those of eyes without BBG.

Mass spectrometry is a widely used technique for identifying molecules in a variety of applications, including organic synthesis and metabolomics. Recently,a deep neural network model for mass spectrometry has been developed and numerically assessed. However, we confirmed that the model performs poorly for a specific target such as highly-fluorinated compound, this study introduces a simple dataset undersampling scheme using a molecular similarity. The model trained on the undersampled dataset shows that the predictive performance was improved for fluorinated compounds and was relatively maintained even for non-fluorinated compounds. This performance is probably ascribed to the reduction of bit collisions of ECFPs. The undersampling approach is general and applicable to any specific target.

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is an important analysis technique that can gather vast amounts of information from surfaces. Recently, machine learning was combined with ToF-SIMS to successfully extract useful information from mass spectra. However, the descriptor generation required for ToF-SIMS analysis using machine learning remains challenging because it requires a lot of effort, is time-consuming, and significantly limits the versatility and practicality of the machine learning approach for ToF-SIMS analysis. Herein, we proposed a new approach to avoid the descriptor generation: to regard ToF-SIMS spectra as images and apply the convolutional neural network (CNN) to analyze these spectral images. We applied and assessed this approach for the identification of silane coupling agents in multicomponent films. Furthermore, the CNN showed higher accuracy than descriptor-based approaches, suggesting its usefulness in achieving the automation and standardization of the ToF-SIMS analysis.

Molecular dynamics simulations were employed to investigate the adsorption behavior of a variety of amino-acid side-chain analogs (SCAs) and a β-hairpin (HP7) peptide on a series of liquid-like self-assembled monolayers (SAMs) with terminal functional groups of –OH, –OCH3, –CH3, and –CF3.

The molecular-type Class II potential functions for classical MD can simulate structure and dynamics of sulfide compounds with any fractions of polyatomic anions.

Metamorphopsia is an important visual symptom of macular disease. We determined predictors for metamorphopsia investigating the relationships of macular hole (MH) diameter and retinal layer thicknesses with metamorphopsia after MH surgery. Forty-two eyes of 42 consecutive patients undergoing MH surgery were retrospectively studied. Metamorphopsia was measured with M-CHARTS. Inner nuclear layer (INL) and outer retinal layer (OR) thicknesses were measured 1000 µm away from central fovea at using Spectralis. Preoperative M-CHARTS scores correlated with MH diameters (P = 0.007–0.031) and changes of temporal OR thickness (P = 0.008–0.010). Postoperative M-CHARTS score at 3 months correlated with preoperative nasal and inferior OR thicknesses (P = 0.003 and 0.016) and with changes of superior INL at 3 and 6 months (P = 0.011 and 0.025), and score at 1 month with change of temporal OR at 6 months (P = 0.033). Postoperative improvement of M-CHARTS scores correlated with changes of temporal INL and superior OR (P = 0.026 and 0.002). Multiple regression analysis revealed that MH diameter was a significant predictor for metamorphopsia. Photoreceptor displacement and inner retinal change may generate metamorphopsia in MH undergoing surgery, however MH diameter is the most powerful predictor.

We examined specimens from the winter–spring cohort of the neon flying squid Ommastrephes bartramii caught off the coast of northeastern Japan in early summer and the following winter for mantle length, sex, maturity, and age to determine their hatching dates as well as their growth and migration patterns. Squid specimens were collected with a research driftnet in July 2018 in the northwestern Pacific and by squid jigging off the coast of northeastern Japan in November 2018 and January 2019. The ages of 300 specimens were estimated from statolith increment counts and used to back-calculate hatching dates. Hatching dates ranged from September 2017 to July 2018. The peak hatching dates varied with the survey season, even for the same winter–spring cohort. Squid caught in July 2018 hatched mainly from February to April, while those caught in November 2018 hatched mostly during April and May and those caught in January 2019 hatched principally during May and June. This pattern indicates that squid migrate among fishing grounds and that stocks are gradually replaced by late-hatching squid.

Vital dyes are frequently used to visualize the internal limiting membrane (ILM) of the neuroretina. This study evaluated and compared the microstructure of the inner retina and visual function with and without brilliant blue G (BBG) staining for ILM peeling during idiopathic epiretinal membrane (ERM) surgery. Retrospective, consecutive, interventional case series. Fifty-five patients (55 eyes) with ERM underwent ILM peeling without dyes (non-dye group) and 55 patients (55 eyes) underwent ILM peeling with BBG staining (BBG group). The logMAR visual acuity (VA) and ganglion cell complex (GCC) thickness were measured using optical coherence tomography at baseline and 12 months after surgery. LogMAR VA improved significantly in both groups at 12 months and the BBG group tended to be better than the non-dye group but with no significant difference between the groups (unpaired t-test, P = 0.490). The average GCC thickness significantly decreased in both groups; however, there was no difference in the rates of change in GCC thickness between the groups. The ratio of GCC thickness to total retinal thickness (%) was significantly higher in the BBG group in the superior quadrant at 12 months postoperatively (P = 0.010). BBG-assisted ERM surgery resulted in better visual improvement and fewer structural changes in the inner retinal layers. BBG-assisted ILM peeling is safe both functionally and anatomically.

Ion transport and the associated structures in glass materials are of interest in batteries and related materials. Herein, the atomic structures and dynamics of Li+ in borosilicate glasses with hig...

To examine 1-year outcomes of metamorphopsia and tangential retinal displacement after epiretinal membrane surgery and identify predictors for metamorphopsia score at 1 year and its improvement from baseline.M-CHARTS were used to measure metamorphopsia. Distances between the intersections of two sets of retinal vessels were measured with infrared or autofluorescence images. Predictors for metamorphopsia scores at 1 year after surgery and their differences from baseline were identified with multivariate regression analysis.Ninety-two eyes of 90 consecutive patients were included. The vertical and horizontal distances continued expanding for 1 year ( P0.001). Both vertical and horizontal metamorphopsia scores improved 3 months after surgery ( P = 0.025 and P0.001, respectively), and horizontal scores continued improving for a year. Horizontal metamorphopsia scores correlated with retinal displacement more strongly than vertical scores. Higher metamorphopsia score at baseline is predictive for that at 1 year. Older age and being male are predictive for less improvement of the score at 1 year from baseline.Metamorphopsia correlates with tangential retinal displacement at 1 year after epiretinal membrane surgery. Horizontal metamorphopsia scores keep improving until 1 year postoperatively. Being male and older age are both independent predictors for poor improvement of metamorphopsia after epiretinal membrane surgery.

Lithium thiophosphate electrolyte is a promising material for application in all-solid-state batteries.

A drastic increase in catalyst turnover number (TON) was accomplished in the cross-metathesis of tetrafluoroethylene (TFE) and vinyl ethers. Under a continuous flow of TFE, catalyst Ru7, which contains a seven-membered N-heterocyclic carbene (NHC) ligand, reached a TON of 4100; this is 2 orders of magnitude higher than the highest hitherto reported value. Mechanistic studies revealed that the expanded NHC successfully destabilizes the stable intermediates with a difluorocarbene structure, which strongly promotes the reaction.

To determine the relationship between the subfoveal choroidal thickness (SCT) and intraocular pressure (IOP) following 25-gauge (25G) and 23-gauge (23G) vitrectomy for idiopathic epiretinal membrane (ERM). Retrospective, consecutive, interventional case series. Sixty-two patients undergoing 25G vitrectomy and 56 patients undergoing 23G vitrectomy for ERM participated. SCT was measured using enhanced depth imaging optical coherence tomography and IOP were measured both at baseline and postoperatively. In both groups, the IOPs on day one and one week after surgery were significantly lower than at baseline (P < 0.001 for both). The rates of changes of IOP were significantly greater in 23G compared to 25G on day one (P = 0.026). In 23G the SCTs on day one and one week after surgery were significantly thicker (P < 0.001) than baseline. The rates of changes in SCT between baseline and day one negatively correlated with those of IOP in 23G (r = −0.559, P < 0.001) but no correlation was observed with 25G (r = −0.129, P = 0.316). Choroidal thickness increases soon after 23G vitrectomy for ERM which is probably due to the transient hypotony, however, early SCT change does not appear in 25G vitrectomy. Twenty-five-gauge vitrectomy may have an advantage in minimizing postoperative choroidal changes.

The aim of this multicenter phase 2 trial, Stop Nilotinib (NILSt), was to examine the safety and efficacy of discontinuation of nilotinib in patients with chronic phase (CP)-chronic myelogenous leukemia (CML). Patients with CP-CML who had achieved molecular response (MR4.5) after initiation of imatinib or nilotinib therapy received consolidation therapy with nilotinib 300–400 mg twice daily for up to 24 months. Patients who maintained MR4.5 at 24 months of consolidation therapy proceeded to discontinuation of nilotinib. The study enrolled 149 patients; 112 patients proceeded to consolidation therapy with nilotinib; 90 patients maintained MR4.5 with consolidation therapy, and 87 proceeded to discontinuation of nilotinib. The treatment-free remission (TFR) (MR4.5) rate at both 1 and 3 years after discontinuation of nilotinib was the same, at 60.9% (90% CI 51.6–69.7). Among 34 patients with molecular relapse, nilotinib was resumed in 33 patients; all of them attained MR4.5. There was no significant association between molecular relapse and age, sex, Sokal score, previous interferon-α exposure, duration of tyrosine kinase inhibitors treatment, or trough concentration of nilotinib. With nilotinib, it might be possible to avoid prognostic factors for TFR that exist with imatinib discontinuation. Cessation of nilotinib after two years of consolidation was safe and feasible. Trial registration UMIN000007141.

Extensive exploration of new non-fullerene acceptor materials in organic photovoltaics has led to enhancements in their power conversion efficiency. However, a comprehensive search for new non-fullerene acceptors with a detailed investigation of non-fullerene organic photovoltaic interface geometries has not been performed. In this study, we theoretically searched for new non-fullerene acceptors, modeled the interface of a non-fullerene acceptor and polymer, and estimated electron transfer rates for charge transfer and charge recombination processes via the Marcus formula. By examining more than 1850 candidate materials, promising acceptors were found. The theoretical investigation of the interface geometry revealed that steric hindrance restricts the possible interface geometries. Examination of the electron transfer rates suggested that the charge transfer process is more dominant than the charge recombination one, which is advantageous for high power conversion efficiency.

PURPOSE To investigate the correlations of thickness of three retinal layers with retinal displacement after idiopathic macular hole surgery. STUDY DESIGN Retrospective, consecutive, case series. METHODS 42 eyes of 42 patients undergoing macular hole surgery with internal limiting membrane peeling were studied. Retinal distance was measured with near-infrared images between the optic nerve and the intersection of retinal vessels at four quadrants. Retinal thicknesses of inner retinal layer, inner nuclear layer and outer retinal layer were measured 1000 μm away from the central fovea using Spectralis. RESULTS Retinal distances other than the nasal quadrant decreased postoperatively (p

Vital dyes are frequently used to visualize the internal limiting membrane (ILM) of the neuroretina. This study evaluated and compared the microstructure of the inner retina and visual function with and without brilliant blue G (BBG) staining for ILM peeling during idiopathic epiretinal membrane (ERM) surgery.Retrospective, consecutive, interventional case series.Fifty-five patients (55 eyes) with ERM underwent ILM peeling without dyes (non-dye group) and 55 patients (55 eyes) underwent ILM peeling with BBG staining (BBG group). The logMAR visual acuity (VA) and ganglion cell complex (GCC) thickness were measured using optical coherence tomography at baseline and 12 months after surgery.LogMAR VA improved significantly in both groups at 12 months and the BBG group tended to be better than the non-dye group but with no significant difference between the groups (unpaired t-test, P = 0.490). The average GCC thickness significantly decreased in both groups; however, there was no difference in the rates of change in GCC thickness between the groups. The ratio of GCC thickness to total retinal thickness (%) was significantly higher in the BBG group in the superior quadrant at 12 months postoperatively (P = 0.010).BBG-assisted ERM surgery resulted in better visual improvement and fewer structural changes in the inner retinal layers. BBG-assisted ILM peeling is safe both functionally and anatomically.

A programmable quantum device that has a large number of qubits without fault-tolerance has emerged recently. Variational Quantum Eigensolver (VQE) is one of the most promising ways to utilize the computational power of such devices to solve problems in condensed matter physics and quantum chemistry. As the size of the current quantum devices is still not large for rivaling classical computers at solving practical problems, Fujii et al. proposed a method called "Deep VQE" which can provide the ground state of a given quantum system with the smaller number of qubits by combining the VQE and the technique of coarse-graining [K. Fujii, et al, arXiv:2007.10917]. In this paper, we extend the original proposal of Deep VQE to obtain the excited states and apply it to quantum chemistry calculation of a periodic material, which is one of the most impactful applications of the VQE. We first propose a modified scheme to construct quantum states for coarse-graining in Deep VQE to obtain the excited states. We also present a method to avoid a problem of meaningless eigenvalues in the original Deep VQE without restricting variational quantum states. Finally, we classically simulate our modified Deep VQE for quantum chemistry calculation of a periodic hydrogen chain as a typical periodic material. Our method reproduces the ground-state energy and the first-excited-state energy with the errors up to O(1)% despite the decrease in the number of qubits required for the calculation by two or four compared with the naive VQE. Our result will serve as a beacon for tackling quantum chemistry problems with classically-intractable sizes by smaller quantum devices in the near future., Comment: 18 pages, 5 figures

Optically active small organic molecules are computationally designed using the ChemTS python library developed by Tsuda and collaborators, which utilizes a combined Monte Carlo tree search (MCTS) and recurrent neural network model. Geometry optimization and excited-state calculations are performed for each generated molecule, following which the excitation energy and dissymmetry factors are computed to evaluate the score function in the MCTS process. Using this procedure, molecules not contained in existing databases are generated. Molecules having either high dissymmetry factors or high transition dipole strengths can be generated depending on the choice of the score function. In a single trajectory with 100,000 trials, mutually similar high-scoring molecules are generated frequently after the initial 15,000-20,000 trials. This indicates that it is better to sample high-scoring molecules from several trajectories having a modest number of trials each than from a single trajectory having a large number of trials.

Polymethine dyes have been utilized in various applications, including optical functional materials. The maximum absorption wavelength ( λ max ) of polymethine dyes is the key for designing optical functional materials. However, there have been few theoretical studies on λ max , especially in the near-infrared region. Therefore, using time-dependent density functional theory (TD-DFT), we calculated the excited states of 70 polymethine dyes with λ max ranging in the visible-to-near infrared region. We also compared these calculated λ max values with experimental ones, using linear regression analysis, and confirmed a strong correlation between the experimental and theoretical λ max values when the portion of the Hartree-Fock exchange in exchange–correlation functionals is relatively high. Linear regression analysis revealed that the experimental λ max values of the polymethine dyes can be quantitatively estimated by combining the TD-DFT calculations with the regression curves. Although several polymethine dyes may exhibit different behaviors at λ max , we could categorize these dyes into a few groups and estimate their excitation energies using regression curves suitable for the respective groups.

We theoretically studied the electronic and magnetic properties of the exterior functionalized endohedral metallofullerenes (EMFs) of Gd2@ I h-C80-X (where X is the exterior functional group). Molecular orbital analysis suggests that the presence of unpaired electron on the I h-C80 cage is not favoring the observation of stable species. One of the effective strategies to address this problem is by attaching an exterior functional group to the fullerene cage. Out of the studied exterior functionalized EMFs, we were successful in finding two stable species such as Gd2@ I h-C80-CF3 and Gd2@ I h-C80-C3N3Ph2 with no unpaired spin on the cage. Further, we utilized exterior functional groups such as -CF3 (1) and -C3N3Ph2 (2) to model and to stabilize dinuclear Dy2@ I h-C80 species, and we thoroughly investigated their magnetic properties using ab initio calculations. Within the single-ion paradigm, DyIII ions in 1 and 2 are magnetically anisotropic, and their magnetization-reversal energy barriers are estimated to be ∼698 and ∼705 cm-1, respectively. Furthermore, beyond the single-ion paradigm, i.e., considering a ferromagnetic coupling (∼30 cm-1) between the lanthanide ions and the radical spin, the energy barriers of 1 and 2 are estimated to be 79.8 and 73.0 cm-1, respectively.

Acute panmyelosis with myelofibrosis (APMF) is a rare subtype of acute myeloid leukemia characterized by acute onset of cytopenias and bone marrow fibrosis in the absence of splenomegaly. Because the prognosis of APMF is extremely poor even after chemotherapy, hematopoietic cell transplantation (HCT) has been used to treat APMF. However, the outcome after HCT for APMF remains unclear. To evaluate the outcomes and prognostic factors after HCT as a therapeutic modality for APMF, we retrospectively analyzed the Japanese registration data of 40 APMF patients who received allogeneic and syngeneic HCT between 2005 and 2015. The median age at HCT was 53.5 years (range, 16 to 70). The disease status at HCT was first complete remission (CR1) in 13 patients (33%). The probability of overall survival and the cumulative incidence of relapse at 3 years were 24% and 59%, respectively. Univariate analysis identified that female sex and disease status CR1 at the time of HCT were significantly associated with higher overall survival. Although APMF patients have a poor long-term prognosis even after syngeneic and allogeneic HCT, these data suggested that allogeneic HCT offered a curative option for APMF.

It is essential for the design and optimization of optoelectrical devices to control the heterointerfacial structures of electron-donor and -acceptor materials at the molecular level because it is here that critical photophysical processes occur. In the present study, we have demonstrated that the accommodation of polythiophene and fullerene without any peripheries in one-dimensional nanochannels of a porous coordination polymer (PCP) enabled selective formation of end-on orientation relative to polythiophene–fullerene interfaces. We studied the charge-carrier dynamics of the one-dimensional assemblies of polythiophene and fullerene confined in the PCP. It is noteworthy that a long-lived charge-separated state arises uniquely in the end-on orientation. Theoretical analysis showed a small electron coupling between polythiophene and fullerene in the end-on orientation, suppressing charge recombination and prolonging the charge-carrier lifetime.

This study has proposed a Huckel theory-based extrapolation scheme for estimating the highest occupied molecular orbital (HOMO)-the lowest unoccupied molecular orbital (LUMO) gap of polymers without resorting to periodic boundary condition calculations using plane wave functions with hybrid functionals. The extrapolation scheme similar to ONIOM combines pure density functional theory (DFT) using plane wave functions for polymers and hybrid DFT using Gaussian functions for oligomers. We numerically assessed the scheme for polythiophene and 380 polymers and confirmed its accuracy and efficiency for polymer screening. Therefore, this scheme can be a screening methodology to estimate HOMO-LUMO energy gaps.

The organic cation dynamics in organic–inorganic hybrid perovskites affect the unique physical properties of these materials. To date, the rotational dynamics of methylammonium (CH3NH3+) and formamidinium (CH(NH2)2+) have been studied both experimentally and from first-principles calculations. Recently, a novel hybrid perovskite with large organic cation guanidinium (C(NH2)3+, GA), which exhibited extraordinarily long carrier lifetimes, was reported. In order to analyze physical properties of GA, we examined the detailed rotational potential energy surfaces and rotational energy barriers of GA in cubic-phase GASnI3 and alternative perovskites using first-principles calculations. The analysis revealed that the principal rotations of GA involve six hydrogen bonds between the organic cation and the inorganic framework in the crystals. Our results suggest that GA can effectively passivate under-coordinated iodine ions using its high hydrogen bond capability, which is consistent with the experimental speculati...

Organic–inorganic metal halide perovskites (MHPs) exhibit prominent electronic and optical properties benefiting the performance of solar cells and light-emitting diodes. However, the dielectric properties of these materials have remained poorly understood, despite probably influencing delayed charge recombination and device capacitance. Herein, we characterize the unprecedented dielectric behavior of MHPs comprising methylammonium cations, Pb/Sn as metals, and Br/I as halides using time-resolved microwave conductivity (TRMC) measurements. At specific compositions, the above MHPs exhibit negative real and positive imaginary photoconductivities, the polarities of which are opposite those observed for conventional photogenerated charge carriers. Comparing the observed TRMC kinetics with that of inorganic perovskites (SrTiO3 and BaTiO3) and characterizing its dependence on temperature, frequency, and near-infrared second push pulse, we conclude that the above behavior is due to the trapping of polaronic hole...

To determine the changes in retinal thickness and whether they correlate with the size of the macular hole (MH) after vitrectomy with internal limiting membrane peeling. Retrospective, interventional case series Consecutive patients with an MH and undergoing pars plana vitrectomy with internal limiting membrane peeling were studied. The retinal thicknesses in the inner 4 sectors as defined by the Early Treatment of Diabetic Retinopathy Study were measured using spectral-domain optical coherence tomography (SD-OCT) before and at 2 weeks and 1, 3, 6, and 12 months after the surgery. The basal and minimum diameters of the MHs were measured. The correlations between the retinal thicknesses and the size of the MH were determined. Thirty-three eyes of 32 consecutive patients (18 women; mean age, 64.2 ± 8.8 years) with an MH were studied. Thirteen eyes had a stage-2 MH; 12 eyes, a stage-3 MH; and 8 eyes, a stage-4 MH. The mean retinal thickness in the temporal sector was 362.8 ± 29.9 µm preoperatively, 337.9 ± 20.6 µm at 2 weeks postoperatively, and 307.6 ± 20.2 µm at 12 months postoperatively (P < .001 for both, paired t tests). The respective mean thicknesses in the superior, inferior, and nasal sectors were 373.9 ± 34.9, 367 ± 28.7, and 385.5 ± 35.9 µm preoperatively; 361.6 ± 22.7, 359.4 ± 20.6, and 383.4 ± 29.0 µm at 2 weeks postoperatively (P = .0087, P = .049, P = .635); and 339.4 ± 18.9, 331.6 ± 21.4, and 371.3 ± 23.2 µm at 12 months postoperatively (P < .001, P < .001, P = .033). The changes in the retinal thickness at 2 weeks and 12 months in all 4 sectors were significantly correlated with the basal and minimum diameters of the MH. Retinal thinning was observed soon after the MH surgery mainly in the temporal sector but also in the superior and inferior sectors. The thinning was greater in eyes with a larger MH, indicating that retinal structures dynamically change after internal limiting membrane peeling.

A theoretical search for organic photovoltaic materials is immensely helpful for easily identifying candidate materials and ultimately achieving high power conversion efficiencies for solar cells. In this study, an automatic scheme for screening organic photovoltaic (OPV) materials has been developed. This scheme mainly includes three steps, namely, the automatic generation of thiophene-based semiconducting polymers composed of donor and acceptor units, estimation of orbital levels by Huckel-based models, and an evaluation of photovoltaic characteristics. A numerical assessment confirmed that the screening tool could be applied to any calculations with a basis set that includes diffuse functions. An examination of 380 donor–acceptor-type polymers demonstrated that the geometric effects such as effective conjugation length and distortion in the polymers affected the orbital levels and were important to consider in the scheme for screening an ideal OPV material. In addition, the photovoltaic characteristics...

Structural and electronic properties on neutral and anionic species of M1M2@Ih-C80 including heteronuclear metal/lanthanides were theoretically investigated. Theoretical analysis demonstrates that M1M2@Ih-C80 can be categorized into three groups: (i) LaM@Ih-C80 (M = Ce, Pr), (ii) LaM@Ih-C80 (M = Sm, Eu), and (iii) GdM@Ih-C80 (M = Sc, Y, La, Lu). Molecular orbital analysis suggests that electron transfer from metal to cage is different for three groups because of the energy level of the metal-based molecular orbital and inherent oxidation state of metals. Thus, choosing suitable combinations of the heterometals for the encapsulation is an effective way to control the stability of M1M2@Ih-C80. The anionization can also stabilize the M1M2@Ih-C80 complexes, as confirmed for homonuclear cases. In addition, we found that the absorption spectra for the studied heterodimetallofullerenes are nearly independent of the metals encapsulated because the π → π* transitions on the cage are dominant even though metal orbi...

The organic cation dynamics in organic–inorganic hybrid perovskites strongly affect the power energy conversion and unique physical properties of these materials. To date, the first-principles rotational potential energy surface (PES) of formamidinium (FA) has not been reported. Thus, we examined the rotational energy barriers for FA in cubic-phase perovskites (FABX3 (B = Sn/Pb; X = Cl/Br/I)) by density functional theory and compared these with those of methylammonium. The calculated rotational PES of FAPbI3 indicates that FA rotates around the N–N bond axis (φ) with a low energy barrier, whereas the energy barrier for FA rotation around the axis penetrating the C atom and the center of gravity of FA (θ) is high. Moreover, the φ and θ rotational barriers of FA increase with halogen substitution. Thus, we reveal important design rules for controlling the rotational barrier and orientation by forming hydrogen bonds and halogen substitution.

Habitat suitability index (HSI) models were applied to identify the potential habitat distribution of the neon flying squid (Ommastrephes bartramii) off the eastern coast of Japan during winter. We used an ocean reanalysis product, a satellite-derived dataset, and commercial fisheries data during 2003–2008 to develop the HSI models, and illustrated the characteristics of the ocean environments at the fishing ground of the neon flying squid, focusing on a typical fishing ground formation event in 2006. The estimated HSI fields of the neon flying squid using three-dimensional (3D) ocean environmental parameters showed a clear relationship between the squid habitat and the edge of a warm core ring south of the Oyashio water; this is considered a key characteristic of fishing ground formation, as noted in Sugimoto and Tameishi (Deep-Sea Research, 39, 1992 and S183). This result suggests that mixing of the warm and nutrient-poor Kuroshio water and the cold and nutrient-rich Oyashio water at the edge of the ring could provide favorable conditions for the foraging of the neon flying squid. The warm water condition in the subsurface layers could be a further advantage to the formation of a stable fishing ground for the neon flying squid. Comparison of the Akaike Information Criteria among a satellite-data-based model, a reanalysis-based model using the same parameters as the satellite-based model, and a reanalysis-based model using 3D ocean environmental parameters, showed an apparent improvement in the performance of the reanalysis-based model using the 3D parameters, reproducing realistic features of the squid fishing ground during the winter of 2006.

PurposeTo determine the correlation of the degree of aniseikonia with the retinal displacements and metamorphopsia in patients that have undergone successful epiretinal membrane (ERM) surgery.MethodsSubjects were 28 eyes with an ERM in 28 patients. The New Aniseikonia Test (NAT) and M-CHARTS were used to quantify the degree of preoperative and postoperative aniseikonia and metamorphopsia. We also evaluated the distance between the intersections of 2 sets of retinal vessels situated vertically or horizontally by using spectral-domain optical coherence tomography (SD-OCT) images in 28 patients.ResultsThe vertical score of M-CHARTS (MV) was not significantly improved, but the horizontal score of M-CHARTS (MH) was significantly improved at 1 week, 1 month, and 3 months postoperatively. The preoperative NAT score was significantly correlated with the preoperative MH. The NAT score at 3 months was significantly correlated with the MH at 3 months and the MV at 3 months. The preoperative NAT score was significantly correlated with the ratio of the vertical retinal displacement at 1 month and at 3 months after surgery. However, the NAT scores did not improve significantly at any postoperative times.ConclusionsThe degree of aniseikonia was significantly correlated with the degree of metamorphopsia and the tangential displacement of the retina after ERM surgery. Aniseikonia is difficult to improve and metamorphopsia may be a more sensitive parameter to detect the functional recovery after successful ERM surgery.

We present a theoretical study on the structural and electronic properties of a series of neutral and anionic species of M2@Ih-C80 (M = Sc, Y, La, Gd, Lu). Molecular orbital analysis suggests that the unpaired electron appears on the cage for neutral M2@Ih-C80 (M = Y, Gd, Lu), and is governed by the level of a metal-based (interstitial) orbital. We showed that anionization is an effective means to stabilize the neutral dimetallofullerenes because of the disappearance of the unpaired electron on the cage. Our theoretical studies on the paramagnetic di-EMF reveals that a strong ferromagnetic interaction is possible for [Gd2@Ih-C80]−. We have also investigated the absorption spectra and found that the anions [M2@Ih-C80]− with the D2h cage symmetry result in similar absorption spectra irrespective of the kinds of metals present (M = Y, La, Gd), while the absorption spectrum for [Sc2@Ih-C80]− with the strong interaction between the Sc metal and cage, which leads to the C2h symmetry, is different from those of D2h.

Organic cation dynamics in organic–inorganic hybrid perovskite such as CH3NH3PbI3 have been reported to play an important role in the charge carrier lifetime and ferroelectricity but have not been fully investigated by theoretical approach. We have compared the rotational energy barriers and relaxation times of the methylammonium cation (CH3NH3, MA) in the cubic phases of MABX3 (B = Pb or Sn, X = Cl, Br, or I) by considering full relaxation of the PbX6 or SnX6 inorganic framework from first principles. We successfully reproduced the experimental rotational barrier for the 4-fold rotational symmetry (C4) of the C—N axis of MA. Our calculations suggest that the MA can rotate relatively freely because the flexible inorganic framework exhibits liquid-like behavior, which induces cooperative displacement of the metal cation (B) and the halogen (X) via a hydrogen bond and lowers the rotational barrier height. We also demonstrate that the rotational barrier of MA (6–11 kJ mol–1), which is closely correlated to t...

To determine whether the degree of metamorphopsia significantly correlated with the distance of the tangenital retinal displacement after epiretinal membrane surgery. The M-CHARTS were used to measure the vertical metamorphopsia score and the horizontal score. The distances between the intersections of two sets of retinal vessels situated vertically or horizontally were measured in the near-infrared Spectralis images. Fifty eyes of 50 patients (22 men; age, 69.5 ± 7.8 years) were retrospectively studied. The vertical and horizontal metamorphopsia scores significantly improved at 1 month after the surgery, and the vertical and horizontal retinal distances increased. The baseline horizontal and vertical metamorphopsia scores significantly correlated with the ratio of the pre- and postoperative vertical and horizontal retinal displacements, respectively (P = 0.038 and P = 0.015 at 1 week; P = 0.036 and P = 0.036 at 1 month). The postoperative horizontal metamorphopsia score at 1 month and the vertical metamorphopsia score at 3 months significantly correlated with the vertical displacement at 1 month (P = 0.034) and the horizontal displacement at 3 months (P = 0.001), respectively. The degree of metamorphopsia significantly correlated with the tangential retinal displacement. Dislocated Muller cells may stimulate the photoreceptors located away from original positions, which consequently results in the sensation of metamorphopsia in patients with an epiretinal membrane.

The effects of stem cell transplantation (SCT) in patients with peripheral T-cell lymphoma not otherwise specified (PTCL-NOS) and angioimmunoblastic T-cell lymphoma (AITL) remain controversial. We analyzed the feasibility of SCT and risk factors associated with outcomes of PTCL-NOS and AITL patients to identify the potential clinical efficacy of SCT. We retrospectively analyzed the data of PTCL-NOS (n = 83) and AITL (n = 112) patients who received autologous (n = 10 and 16, respectively) or allogeneic (n = 12 and 4, respectively) SCT, or no SCT (n = 61 and 92, respectively) between 2008 and 2018. All PTCL-NOS and AITL diagnoses were reconfirmed by an experienced hematopathologist. Median age at PTCL-NOS and AITL diagnoses in the SCT group was younger than that in the no SCT group. Significant risk factors for lower overall survival were intermediate–high and high-risk international prognostic indexes in PTCL-NOS patients (P = 0.0052), and a > 2 modified prognostic index for T-cell lymphoma (P = 0.0079) and no SCT (P = 0.028) in AITL patients. Autologous or allogeneic SCT compared with no SCT in AITL patients resulted in 3-year overall survival of 68.6% and 100% vs. 57.2% (P = 0.018). Strategies should be developed to improve selection of PTCL-NOS and AITL patients suitable for SCT and/or additional novel therapies.

Perovskite solar cells based on lead-halide perovskites have attracted significant attention as prime candidates for next-generation solar cells because of their high-power conversion efficiency. To avoid the toxicity of lead-based perovskites, alternatives such as tin-halide perovskite have been investigated. However, the photovoltaic performance of these alternatives is relatively low, and novel perovskites with low cost, low toxicity, and high performance have not yet been discovered. In this study, to investigate whether promising alternative perovskites exist, a high-throughput material search scheme based on materials informatics was developed and performed for perovskite solar cell materials. Using this scheme, over 28 million $A{A}^{\ensuremath{'}}B{B}^{\ensuremath{'}}{X}_{3}{X}_{3}^{\ensuremath{'}}$ double-perovskite-like compositions were screened. Among the 24 most promising candidates identified, 5 were well-known organic-inorganic tin-halide perovskites and 17 were sodium-, potassium-, and ammonium-based tin-halide perovskites. Interestingly, two transition-metal-based perovskites were also identified as promising solar cell materials. The pioneering material search scheme reported is expected to find use in the identification of practically feasible materials for a number of real-world applications.

Rationale Ecthyma gangrenosum (EG) is an uncommon cutaneous infection usually associated with Pseudomonas aeruginosa bacteremia in immunocompromised patients, particularly those with underlying malignant diseases. Despite its rarity, especially in immunocompetent or nondiagnosed immunodeficiency patients, EG can present as the first manifestation of an underlying immunosuppression. Patient concerns A 42-year-old Japanese man was admitted to our hospital with a 3-day history of a painless red macule on his right forearm and fever. Diagnoses Blood culture on admission revealed the presence of Pseudomonas aeruginosa, whereas pus culture of the skin lesion showed Pseudomonas aeruginosa and methicillin-susceptible Staphylococcus aureus positivity. Interventions Additional bone marrow aspirate examination and immunophenotyping were performed to confirm the diagnosis of acute promyelocytic leukaemia with PML-retinoic acid alpha receptor. Outcomes The patient was successfully treated with a 14-day course of antibiotics, and no evidence of relapse was noted. The patient achieved complete remission after treatment for acute promyelocytic leukaemia. Lessons It should be kept in mind that EG is an important cutaneous infection that is typically associated with P aeruginosa bacteremia and the presence of underlying immunodeficiency, such as acute leukaemia.

The bulk heterojunction organic solar cell has shown much promise as a cost-effective energy harvesting device, while despite recent progress in boosted power conversion efficiency, critical photophysical process at the interface of electron donor and electron acceptor is subject of ongoing debate. Here we investigate the impact of polymer orientation of cychlopentadithiophene–benzothiadiazole copolymer (PCPDTBT) on the charge separation (CS) and recombination (CR) at the bilayer heterojunction of polymer and methanofullerene (PCBM). The charge carrier dynamics at contrasting face-on-rich or edge-on interface controlled via side-alkyl chain modification are monitored by flash-photolysis time-resolved microwave conductivity (TRMC). The data are analyzed using singlet exciton diffusion to donor–acceptor interface with quenching term at high excitation density. We show that CS is more efficient for the face-on-rich interface than edge-on, while CR is in turn retarded for the latter. Along with computational ...

Density functional theory (DFT) calculations were performed to analyse the magnetic properties of dinuclear Ni–Ni and Cu–Cu bis(phenolate)-bridged complexes with two antiferromagnetically-coupled m...

We theoretically investigated the physical properties, including the frontier orbital and excitation energies, for thiophene-based semiconducting polymers composed of donor and acceptor units. Orbital analysis revealed that remarkably different behaviors of frontier orbital energies with respect to the degree of polymerization stems from the distribution of the frontier orbitals, which is insightful information for controlling the ionization potentials and electron affinities of semiconducting polymers. We also successfully estimated the frontier orbital energies of the polymers through a simple Huckel theory-based analytical model parametrized from calculations of relatively small oligomers. This simple model allows us to predict the highest occupied molecular orbital–lowest unoccupied molecular orbital gaps of a polymer at a low computational cost. The simulated absorption spectra of the thiophene-based semiconducting polymers were compared with the experimental spectra. The theoretically designed polym...

We study spin-forbidden transitions of Os polypyridyl sensitizers by two-component relativistic time-dependent density functional theory with the spin–orbit interaction based on Tamm–Dancoff approximation. The absorption spectra, including spin-forbidden-transition peaks, for the Os complexes are reasonably reproduced in comparison with the experimental ones. The extension of the conjugated lengths in the Os complexes is investigated and found to be effective to enhance photo absorption for spin-allowed transitions as well as spin-forbidden ones. This study provides fruitful information for a design of new dyes in terms of conjugation lengths.

We theoretically studied the electronic and magnetic properties of the exterior functionalized endohedral metallofullerenes (EMFs) of Gd

5-Azacytidine (5AC), a hypomethylating agent, is clinically used for the treatment of patients with myelodysplastic syndromes (MDS). Cytidine deaminase (CDA) is a key enzyme in the detoxification of 5AC. We investigated whether the CDA expression could predict response to 5AC in MDS. Among leukemia-derived cell lines, MDS-L, an MDS-derived cell line with a relatively low CDA expression level, was found to be the most sensitive to 5AC. Combination with tetrahydrouridine, an inhibitor of CDA, synergistically potentiated the cytotoxic effect of 5AC. Treatment with 5AC markedly enhanced the expression level of CDA mRNA and showed demethylation at CpG sites in the 5'-flanking region of the CDA gene. We further compared the protein expression levels of CDA in matched clinical samples before and after treatment with 5AC in bone marrow cells from 8 MDS patients by an immunohistochemical analysis. The CDA expression level showed an approximately 2- to 3-fold increase after 5AC treatment in 3 of these cases, and these three patients with relatively higher CDA expression levels after 5AC treatment all showed better clinical responses to 5AC. In contrast, the 5 remaining patients, whose CDA expression showed no augmentation, observed no clinical benefit. Taken together, the optimized determination of the CDA expression levels before and after 5AC treatment, and the methylation status at CpG sites of 5'-flanking region of the CDA gene, may contribute to the development of precise 5AC therapy for MDS.

Optical activity in inorganic colloidal materials was controlled through interactions of chiral molecules with the nanoparticle (NP) surface. An inversion of optical activity in the synthesis of mercury sulfide (HgS) NPs was demonstrated with an intrinsically chiral crystalline system in the presence of an identical chiral capping ligand. A continuous decrease in the positive first Cotton effect and an eventual reversal of CD profile were observed upon heating the aqueous solution of HgS NPs capped with N-acetyl-l-cysteine (Ac-l-Cys) at 80 °C. Ac-l-Cys afforded two bidentate coordination configurations with an almost mirror image of each other using the thiolate and either of carboxylate or acetyl-carbonyl groups on the HgS core. Experiment and calculation suggest that a shift in the distribution of the NP formation with energy in response to the combinations of ligand coordination structure and chiral crystalline surface is responsible for the inversion of optical activity.