Theoretical search for characteristic atoms in supported gold nanoparticles: a large-scale DFT study.

The size and site dependences of atomic and electronic structures in isolated and supported gold nanoparticles have been investigated using large-scale density functional theory (DFT) calculations using multi-site support functions. The effects of the substrate on nanoparticles with diameters of 2 nm and several different shapes have been examined. First, isolated gold nanoparticles with diameters of 0.6 nm (13 atoms) to 4.5 nm (2057 atoms), which have comparable sizes to nanoparticles used in experiments, were considered. To analyse huge amounts of data obtained from large-scale DFT calculations, we performed principal component analysis (PCA), which helps systematically and efficiently clarify the electronic structures of large nanoparticles. The PCA results reveal the site dependence of the electronic structures. Notably, the atoms in the surface and subsurface have different electronic structures to those located in the inner layers, especially at the vertexes of the particles. The convergence of local electronic structures with respect to the particle size has also been demonstrated. For supported nanoparticles, PCA helps indicate which atoms are affected, and how much, by the substrate. The correlation between the PCA results and site dependence of reaction activity is also discussed herein.

Bioinspired Carbonized Polymer Microspheres for Full-Color Whispering Gallery Mode Emission for White Light Emission, Unclonable Anticounterfeiting, and Chemical Sensing Applications.

Light-element-based fluorescent materials, colloidal graphene quantum dots, and carbon dots (CDs) have sparked an immense amount of scientific interest in the past decade. However, a significant challenge in practical applications has emerged concerning the development of solid-state fluorescence (SSF) materials. This study addresses this knowledge gap by exploring the unexplored photonic facets of C-based solid-state microphotonic emitters. The proposed synthesis approach focuses on carbonized polymer microspheres (CPMs) instead of conventional nanodots. These microspheres exhibit remarkable SSF spanning the entire visible spectrum from blue to red. The highly spherical shape of CPMs imparts built-in photonic properties in addition to its intrinsic CD-based attributes. Leveraging their excitation-dependent photoluminescence property, these microspheres exhibit amplified spontaneous emission, assisted by the whispering gallery mode resonance across the visible spectral region. Remarkably, unlike conventional semiconductor quantum dots or dye-doped microresonators, this single microstructure showcases adaptable resonant emission without structural/chemical modifications. This distinctive attribute enables a plethora of applications, including microcavity-assisted energy transfer for white light emission, highly sensitive chemical sensing, and secure encrypted anticounterfeiting measures. This interdisciplinary approach, integrating photonics and chemistry, provides a robust solution for light-element-based SSF with inherent photonic functionality and wide-ranging applications.

Extraction of local structure differences in silica based on unsupervised learning.

Silica exhibits a rich phase diagram with numerous stable structures existing at different temperature and pressure conditions, including its glassy form. In large-scale atomistic simulations, due to the small energy difference, several phases may coexist. While, in terms of long-range order, there are clear differences between these phases, their short- or medium-range structural properties are similar for many phases, thus making it difficult to detect the structural differences. In this study, a methodology based on unsupervised learning is proposed to detect the differences in local structures between eight phases of silica, using atomic models prepared by molecular dynamics (MD) simulations. A combination of two-step locality preserving projections (TS-LPP) and locally averaged atomic fingerprints (LAAF) descriptor was employed to find a low-dimensional space in which the differences among all the phases can be detected. From the distance between each structure in the found low-dimensional space, the similarity between the structures can be discussed and subtle local changes in the structures can be detected. Using the obtained low-dimensional space, the ß-α transition in quartz at a low temperature was analyzed, as well as the structural evolution during the melt-quench process starting from α-quartz. The proper differentiation and ease of visualization make the present methodology promising for improving the analysis of the structure and properties of glasses, where subtle differences in structure appear due to differences in the temperature and pressure conditions at which they were synthesized.

Clinical and safety outcomes of simultaneous bilateral total knee arthroplasty for Japanese octogenarian patients: a retrospective analysis.

PURPOSE: The demand for simultaneous bilateral total knee arthroplasty (SiBTKA) in older adults is expected to increase with an aging population, thus necessitating evaluating its efficacy and safety. However, there is limited information regarding the clinical outcomes of SiBTKA in older adults, particularly in octogenarians. We aimed to assess the clinical outcomes and safety of SiBTKA in Japanese patients aged ≥ 80 years. METHODS: Of the 176 consecutive knees that underwent SiBTKA between July 2016 and January 2022 at our hospital, 172 were selected. They were divided into two groups according to the patient age as follows: the octogenarian group (≥ 80 years, 74 knees) and the younger control group (< 80 years, 98 knees). In addition, we assessed their preoperative clinical information, clinical outcomes using the Knee Society Score for knee (KSS-K) and function (KSS-F), and the incidence of early (≤ 90 days) and late (> 90 days) postoperative complications. RESULTS: The mean follow-up period was 3.5 years. The KSS-K scores of both groups improved postoperatively than that preoperatively. Both preoperative and postoperative KSS-F scores were lower in the octogenarians; however, their improvement rates were similar to those of the younger controls. We observed no significant intergroup differences in early or late postoperative complications, including infection, systemic complications, periprosthetic fractures, aseptic loosening, and mortality. CONCLUSION: SiBTKA for octogenarians had clinical outcomes and postoperative complication incidence similar to that for younger controls. Therefore, SiBTKA may be a safe and effective treatment option for octogenarians with painful bilateral knee deformities.

Determination of hyper-parameters in the atomic descriptors for efficient and robust molecular dynamics simulations with machine learning forces.

The atomic descriptors used in machine learning to predict forces are often high dimensional. In general, by retrieving a significant amount of structural information from these descriptors, accurate force predictions can be achieved. On the other hand, to acquire higher robustness for transferability without overfitting, sufficient reduction of descriptors should be necessary. In this study, we propose a method to automatically determine hyperparameters in the atomic descriptors, aiming to obtain accurate machine learning forces while using a small number of descriptors. Our method focuses on identifying an appropriate threshold cut-off for the variance value of the descriptor components. To demonstrate the effectiveness of our method, we apply it to crystalline, liquid, and amorphous structures in SiO2, SiGe, and Si systems. By using both conventional two-body descriptors and our introduced split-type three-body descriptors, we demonstrate that our method can provide machine learning forces that enable efficient and robust molecular dynamics simulations.

A case of subacute combined degeneration of the spinal cord diagnosed with difficulty due to a history of treatment for pyogenic spondylitis.

Early diagnosis of spinal cord subacute combined degeneration (SCD) is difficult, especially in pre-existing lower extremity impairment cases. We report a case of progressive SCD diagnosed after severe anemia. The peripheral symptoms of SCD other than gait disturbance should also be well understood and given close attention.

Preoperative incidence and risk factors of deep vein thrombosis in Japanese patients undergoing total hip arthroplasty.

PURPOSE: Preoperative deep vein thrombosis (DVT) is a risk factor for postoperative venous thromboembolism (VTE), causing severe mortality. Early detection of preoperative DVT is essential to prevent postoperative VTE. However, little is known regarding preoperative DVT in patients undergoing major surgery. The present study aimed to determine the incidence and risk factors of preoperative DVT in patients admitted for total hip arthroplasty (THA). METHODS: From August 2017 to September 2022, 243 patients admitted for THA at our institution were enrolled in this study. Patients medical records and preoperative laboratory data were retrospectively collected. According to the results of lower-limb ultrasonography, patients were divided into either the non-DVT (n = 136) or DVT (n = 43) group. The incidence of DVT and independent risk factors for preoperative DVT were investigated using univariate and multivariate logistic regression analyses. RESULTS: The mean age was 74.0 ± 8.4 years. Preoperative DVT was diagnosed in 43 of the 243 (17.7%) patients. The risk of DVT was significantly high (p < 0.05) in patients with advanced age, increased D-dimer levels, and malnutrition status, as assessed by the Geriatric Nutritional Risk Index (GNRI). Multivariate analysis showed that advanced age, increased D-dimer level, and malnutrition status assessed by the GNRI were independent risk factors for preoperative DVT. CONCLUSION: A high incidence of preoperative DVT was observed in patients undergoing THA. Advanced age, increased D-dimer levels, and malnutrition assessed by the GNRI increased the risk of preoperative DVT. Screening high-risk subgroups for preoperative DVT is necessary to prevent postoperative VTE.

Correlation of knee laxity with alignment and repetitive physical activity in patients with knee osteoarthritis: A cross-sectional study.

BACKGROUND: Malalignment, knee laxity, and repetitive physical activity are considered biomechanical risk factors for knee osteoarthritis (KOA), though the correlation among these factors is poorly understood. The purpose of this study was to elucidate the relationship between knee laxity and alignment, and to determine the effects of repetitive physical activity on knee laxity in patients with KOA. METHODS: The study subjects were 68 patients with radiographic tibiofemoral KOA and 68 control subjects. Each participant underwent clinical evaluation, muscle strength test, radiography, and knee laxity test. Laxity was evaluated before and after repetitive stepping exercise using tri-axial accelerometer. RESULTS: Mediolateral acceleration correlated (P < 0.01) with two coronal alignments (mechanical axis: hip-knee-ankle angle (HKA); and joint line convergent angle (JLCA)). Pearson correlation coefficient was small (r = 0.23-0.24) before but increased after stepping (r = 0.28-0.33). Increased mediolateral acceleration after stepping correlated with JLCA (r = 0.37, P < 0.001). There were significant differences in coronal alignments, gait speed, mediolateral acceleration, and accelerations in all directions between the control and KOA groups. Anteroposterior acceleration did not correlate with sagittal knee alignment. Multiple logistic regression analysis identified HKA/JLCA, and increased mediolateral acceleration after stepping as significant diagnostic predictors of KOA. CONCLUSIONS: We found a direct relationship between knee laxity and alignment or repetitive physical activity. Repetitive stepping activity significantly increased mediolateral acceleration in KOA patients, compared with the control. Stepping increased the correlation between mediolateral acceleration and coronal alignment. In knees with large JLCA, repetitive stepping caused much larger mediolateral laxity.

Clinical and radiological outcomes of total hip arthroplasty in octogenarian patients using a three-dimensional porous titanium cup: a retrospective analysis in Japanese patients.

PURPOSE: Osteointegration of a three-dimensional (3D) porous titanium material has been experimentally proven, but only a few studies have shown the clinical outcomes of a 3D porous titanium cup in the Japanese elderly population. The purpose of this study was to compare the short-and-medium term clinical and radiographic results of total hip arthroplasty (THA) using a 3D porous titanium cup in patients aged ≥ 80 (octogenarians) versus those aged < 80 (younger controls). METHODS: A total of 104 hips that underwent THA using a 3D porous titanium cup (SQRUM TT, Kyocera Medical) were enrolled in the study and were divided into two groups according to age: the octogenarian group (≥ 80, n = 42) and the younger control group (< 80, n = 62). Furthermore, we evaluated patient characteristics, clinical outcomes determined by the Japanese Orthopedic Association score, cup alignment, and incidence of radiolucent lines around the cup. RESULTS: The mean follow-up period was 4.2 and 4.0 years (p = 0.29) for octogenarians and younger controls, respectively. The clinical outcomes were excellent, and no revision surgery occurred until the last follow-up in both groups. The number of patients with radiolucent lines at the final evaluation was 21 of 62 (33.9%) in younger controls and 16 of 42 (38.1%) in octogenarians. CONCLUSION: THA with 3D porous titanium cup for octogenarians had similar clinical outcomes and incidence of radiolucent lines as those of younger controls, suggesting that the 3D porous titanium cup may be useful in THA for octogenarians. Further investigations will confirm its long-term outcomes.

Effect of Antimicrobial Prophylaxis Duration on Health Care-Associated Infections After Clean Orthopedic Surgery: A Cluster Randomized Trial.

Importance: Postoperative health care-associated infections are associated with a greater deterioration in patients' general health status and social and economic burden, with at least 1 occurring in approximately 4% of acute care hospital patients. Antimicrobial prophylaxis prevents surgical site infections in various orthopedic procedures; however, its relationship with health care-associated infections remains unknown. Objective: To examine whether a shorter antimicrobial prophylaxis duration of less than 24 hours after surgery is not inferior to a longer duration in preventing health care-associated infections after clean orthopedic surgery. Design, Setting, and Participants: This open-label, multicenter, cluster randomized, noninferiority clinical trial was conducted in 5 tertiary referral hospitals in greater Tokyo metropolitan area, Japan, from May to December 2018. Adult patients undergoing clean orthopedic surgery were recruited until the planned number of participants was achieved (500 participants per group). Statistical analysis was conducted from July to December 2019. Interventions: Antimicrobial prophylaxis was discontinued within 24 hours after surgery in group 24 and 24 to 48 hours after surgery in group 48. Group allocation was switched every 2 or 4 months according to the facility-based cluster rule. Study-group assignments were masked from participants. Main Outcomes and Measures: The primary outcome was the incidence of health care-associated infections requiring antibiotic therapies within 30 days after surgery. The noninferiority margin was 4%. Results: Of the 1211 participants who underwent cluster allocation, 633 participants were in group 24 (median [IQR] age, 73 [61-80] years; 250 men [39.5%] and 383 women [60.5%]), 578 participants were in group 48 (median [IQR] age, 74 [62-81] years; 204 men [35.3%] and 374 women [64.7%]), and all were eligible for the intention-to-treat analyses. Health care-associated infections occurred in 29 patients (4.6%) in group 24 and 38 patients (6.6%) in group 48. Intention-to-treat analyses showed a risk difference of -1.99 percentage points (95% CI, -5.05 to 1.06 percentage points; P < .001 for noninferiority) between groups, indicating noninferiority. Results of adjusted intention-to-treat, per-protocol, and per designated procedure population analyses supported this result, without a risk of antibiotic resistance and prolonged hospitalization. Conclusions and Relevance: This cluster randomized trial found noninferiority of a shorter antimicrobial prophylaxis duration in preventing health care-associated infections without an increase in antibiotic resistance risk. These findings lend support to the global movement against antimicrobial resistance and provide additional information on adequate antimicrobial prophylaxis for clean orthopedic surgery. Trial Registration: Identifier: UMIN000030929.

Effects of knee extension exercise starting within 4 h after total knee arthroplasty.

PURPOSE: To determine the beneficial effects of knee extension exercise applied from 4 h after TKA. METHODS: Patients undergoing TKA for osteoarthritis were assigned to early rehabilitation (n = 41) and control rehabilitation (n = 39) groups. Rehabilitation of knee extension exercise was started within 4 h postoperative in the early group and 2 days after surgery in the control group. Joint range of motion and pain were assessed before surgery and at 3 days to 12 months after surgery. Muscle strength and gait parameters were assessed before and 3 weeks after surgery. RESULTS: Extension range of motion was significantly increased in the early group than the control at 3 days, 3 weeks and 6 months after surgery. In gait parameters, peak knee flexion and extension angles during stance phase were significantly improved in the early group than the control group at 3 weeks after surgery. Flexion range of motion was increased in the early group than the control at 12 months after surgery. CONCLUSION: Starting knee extension exercise within 4 h after TKA reduced the early loss of extension range of motion and improved gait pattern and seemed to contribute to be better functional outcome one year after surgery.

Injuries and Illnesses Observed in Athletes from Beginner to Elite Levels at the 18th National Sports Festival for Persons with Disabilities in Japan.

OBJECTIVES: : This study aimed to describe the injuries and illnesses that occurred at the 18th National Sports Festival for Persons with Disabilities in Japan, which was attended by more than 3000 athletes from beginner to elite levels. METHODS: : Records from medical stations set up at the venues for each sport were reviewed. The incidence rates (IRs) were calculated as the number of medical station visits per 1000 athlete-days. The backgrounds of injuries and illnesses were investigated. RESULTS: : In total, 3277 athletes attended the festival, and 134 eligible medical station visits were analyzed. Overall, 102 athletes complained of injuries. For the whole schedule of the festival, IRs were 15.5 for injuries and illnesses and 11.8 for injuries alone. For injuries and illnesses, high IRs were seen in soccer (39.8), basketball (25.6), and foot baseball (22.4); for injuries alone, high IRs were also seen in soccer (33.6), basketball (25.6), and foot baseball (16.8). The most frequent symptoms were internal symptoms (n=32), contusions (n=30), and wounds (n=24). Joint sprains occurred in various sports, whereas muscle strains happened mainly in disciplines demanding sprinting or high agility. Of the 55 cases that occurred during events or public rehearsals, 45 were traumatic, whereas the relation to sports activities was not described in 51 cases. Of participants with internal symptoms, 11 were suggested to have viral infections. We identified 21 injuries caused by falls. CONCLUSIONS: : Minor trauma and viral infection were the most frequently observed symptoms among injuries and illnesses, respectively. Structured medical records and organized surveillance systems should be utilized to improve data collection and understand the onset of injury and illness.

18F-sodium fluoride positron emission tomography may help diagnose nondisplaced peri-prosthetic and peri-implant fracture.

Occult fractures are challenging to diagnose, especially those involving an implant surrounding the suspected fracture site. This is the first case wherein 18F-sodium fluoride positron emission tomography substantially helped to diagnose peri-prosthetic and peri-implant fractures. The application of this imaging modality warrants further study.

The investigation of methane storage at the Ni-MOF-74 material: a periodic DFT calculation.

To develop a high-performance methane storage material, an understanding of the mechanism and electronic interactions between methane and the material is essential. In this study, we performed detailed theoretical analyses to investigate the methane storage capacity of Ni-MOF-74 using a large-scale periodic DFT code CONQUEST. In a single pore of the unit cell, we considered three possible sites, iSBU, L, and P sites, where iSBU is the inorganic secondary building unit with a metal center, and L is the linker consisting of the organic building unit, while the P site is the vacuum site in the center of the pore. It shows that the methane molecule adsorption possesses the largest methane molecule adsorption energy on the iSBU site. Our calculations indicate that both C-HO and weak agostic interactions exist between the methane molecule and the iSBU site. The adsorption energy of one methane molecule on the iSBU site is in good agreement with previous experimental and theoretical studies. The calculation of the stepwise methane molecule adsorption shows that the first six methane molecules can first occupy the iSBU sites via C-HO and weak agostic interactions. The second six methane molecules are adsorbed on the remaining L sites, where the C-Hπ interaction becomes important, leading to the synergistic effect together with the C-HO interaction to enhance the adsorption energy of the methane molecule. Finally, it can adsorb up to sixteen CH4 molecules in a single pore of a unit cell at Ni-MOF-74. Moreover, we conducted DOS and EDD analyses, which clearly show that the interactions play a vital role in the adsorption of a methane molecule on Ni-MOF-74, especially the C-HO interaction.

Intraosseous epidermal cyst of the great toe that was difficult to distinguish from chronic osteomyelitis: A case report and literature review.

Obtaining a correct intraosseous epidermal cyst diagnosis is difficult due to the extreme rarity of this cyst. Further, the clinical manifestations and radiographic findings are very similar to those of a malignancy or infection. Early histopathological analysis is required for accurate diagnosis and for avoiding unnecessary antibiotic administration and amputation.

18F-sodium fluoride positron emission tomography may help determine better treatment for thigh pain after hip arthroplasty-A case report.

Thigh pain after hip arthroplasty is multifactorial; uncovering its etiology is paramount for optimal treatment. This is the first case where 18F-sodium fluoride positron emission tomography substantially helped in diagnosing the post-hip arthroplasty persistent thigh pain and appropriate treatment selection. This imaging modality warrants further study and more widespread application.

Optimization of a Bayesian penalized likelihood algorithm (Q.Clear) for 18F-NaF bone PET/CT images acquired over shorter durations using a custom-designed phantom.

BACKGROUND: The Bayesian penalized likelihood (BPL) algorithm Q.Clear (GE Healthcare) allows fully convergent iterative reconstruction that results in better image quality and quantitative accuracy, while limiting image noise. The present study aimed to optimize BPL reconstruction parameters for 18F-NaF PET/CT images and to determine the feasibility of 18F-NaF PET/CT image acquisition over shorter durations in clinical practice. METHODS: A custom-designed thoracic spine phantom consisting of several inserts, soft tissue, normal spine, and metastatic bone tumor, was scanned using a Discovery MI PET/CT scanner (GE Healthcare). The phantom allows optional adjustment of activity distribution, tumor size, and attenuation. We reconstructed PET images using OSEM + PSF + TOF (2 iterations, 17 subsets, and a 4-mm Gaussian filter), BPL + TOF (ß = 200 to 700), and scan durations of 30-120 s. Signal-to-noise ratios (SNR), contrast, and coefficients of variance (CV) as image quality indicators were calculated, whereas the quantitative measures were recovery coefficients (RC) and RC linearity over a range of activity. We retrospectively analyzed images from five persons without bone metastases (male, n = 1; female, n = 4), then standardized uptake values (SUV), CV, and SNR at the 4th, 5th, and 6th thoracic vertebra were calculated in BPL + TOF (ß = 400) images. RESULTS: The optimal reconstruction parameter of the BPL was ß = 400 when images were acquired at 120 s/bed. At 90 s/bed, the BPL with a ß value of 400 yielded 24% and 18% higher SNR and contrast, respectively, than OSEM (2 iterations; 120 s acquisitions). The BPL was superior to OSEM in terms of RC and the RC linearity over a range of activity, regardless of scan duration. The SUVmax were lower in BPL, than in OSEM. The CV and vertebral SNR in BPL were superior to those in OSEM. CONCLUSIONS: The optimal reconstruction parameters of 18F-NaF PET/CT images acquired over different durations were determined. The BPL can reduce PET acquisition to 90 s/bed in 18F-NaF PET/CT imaging. Our results suggest that BPL (ß = 400) on SiPM-based TOF PET/CT scanner maintained high image quality and quantitative accuracy even for shorter acquisition durations.

Blue moon ensemble simulation of aquation free energy profiles applied to mono and bifunctional platinum anticancer drugs.

Aquation free energy profiles of neutral cisplatin and cationic monofunctional derivatives, including triaminochloroplatinum(II) and cis-diammine(pyridine)chloroplatinum(II), were computed using state of the art thermodynamic integration, for which temperature and solvent were accounted for explicitly using density functional theory-based canonical molecular dynamics (DFT-MD). For all the systems, the "inverse-hydration" where the metal center acts as an acceptor of hydrogen bond has been observed. This has motivated to consider the inversely bonded solvent molecule in the definition of the reaction coordinate required to initiate the constrained DFT-MD trajectories. We found that there exists little difference in free enthalpies of activation, such that these platinum-based anticancer drugs are likely to behave the same way in aqueous media. Detailed analysis of the microsolvation structure of the square-planar complexes, along with the key steps of the aquation mechanism, is discussed.

Large scale and linear scaling DFT with the CONQUEST code.

We survey the underlying theory behind the large-scale and linear scaling density functional theory code, conquest, which shows excellent parallel scaling and can be applied to thousands of atoms with diagonalization and millions of atoms with linear scaling. We give details of the representation of the density matrix and the approach to finding the electronic ground state and discuss the implementation of molecular dynamics with linear scaling. We give an overview of the performance of the code, focusing in particular on the parallel scaling, and provide examples of recent developments and applications.

Author Correction: Gate controlling of quantum interference and direct observation of anti-resonances in single molecule charge transport.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.