Unveiling the Nature of Chemical Bonds in Real Space.

Recent advent of diverse chemical entities necessitates a re-evaluation of chemical bond concepts, underscoring the importance of experimental evidence. Our prior study introduced a general methodology, termed Core Differential Fourier Synthesis (CDFS), for mapping the distribution of valence electron density (VED) in crystalline substances within real space. In this study, we directly compare the VED distributions obtained through CDFS with those derived from high-accuracy theoretical calculation using long-range corrected density functional theory, which quantitatively reproduces accurate orbital energies. This comparison serves to demonstrate the precision of the CDFS in replicating complex details. The VED patterns observed experimentally exhibited detailed structures and phases of wave functions indicative of sp3 hybrid orbitals, closely aligning with theoretical predictions. This alignment underscores the utility of our approach in gathering quantum chemical data experimentally, a crucial step for discussing the chemical properties, such as reaction mechanisms.

Four stem fractures in a 12-year follow-up study of 9,135 patients with Exeter hip stems at seven teaching facilities in Japan.

BACKGROUND: Although excellent long-term results have been reported for the Exeter stem, stem fracture is recognized as a rare complication. However, there have been no reports on the incidence and risk factors for stem fractures based on detailed population information. This study aimed to clarify the incidence of Exeter hip stem fracture based on detailed population information from seven Exeter stem teaching centers in Japan and to examine the risk factors for stem fracture. METHODS: A total of 8,499 primary total hip arthroplasties (THA) and 636 revision hip arthroplasties (revisions) performed at seven Exeter teaching hospitals between 1999 and 2021 were included and retrospectively investigated based on medical records. RESULTS: Stem fractures were identified in two primary THA (fracture rate: 0.02%) and two revision THA (fracture rate: 0.21%) cases. The stem length was ≤125 mm in three out of these four cases. Revision and 30 stem were the risk factors for stem fractures. Weight and body mass index (BMI) were not significantly associated with the occurrence of stem fractures. CONCLUSIONS: In Western countries, the incidence of Exeter stem fractures is reportedly 0.017-0.15% for primary THA and 0.99-1.21% for revision THA. In this study, the incidence of primary THA was 0.02%, which is similar to the lowest reported rate, whereas the incidence of revision THA was 0.21%, which is lower than that reported in previous studies. Revision surgery had the same risk factors as those reported in the West-namely, stem length ≤125 mm (except for the 30 stem) and BMI, which were not risk factors in Japanese patients.

Giant impurity effect on anomalous Hall effect of Mn3Sn.

Mn3Sn is an anomalous Hall effect (AHE) antiferromagnet that exhibits the hysteretic AHE in antiferromagnetic (AFM) phase at room temperature. We report that whisker Mn3Sn crystals grown by the flux method exhibit a non-hysteretic AHE at mid-to-low temperatures when the whisker Mn3Sn is surrounded by a thin layer of ferromagnetic Mn2-xSn. These crystals exhibit a hysteretic AHE above 275 K due to the spin alignment of the inverse triangular lattice, which is similar to other crystals. However, upon cooling the crystal, it exhibits a non-hysteretic AHE with a spiral AFM spin structure at 100-200 K. We concluded that the non-hysteretic AHE is induced at the interface of Mn2-xSn/Mn3Sn. We believe that the scalar-spin chirality in the spiral AFM phase of Mn3Sn, modulated by Mn2-xSn through the magnetic proximity effect, produces the AHE. This discovery opens a new avenue for tailoring the AHE by magnetic layers.

Multi-center study of use of the Exeter stem in Japan: a 10-year follow-up report.

PURPOSE: Since the introduction of the Exeter stem for clinical use in Japan in 1996, the number of stems used has continued to rise owing to its favorable results. We investigated the outcomes of patients who had previously undergone total hip arthroplasty with the Exeter stem in Japan with a 10-year + follow-up period. METHODS: This retrospective cohort study used clinical and radiographic data of 682 cases of primary total hip arthroplasty performed using the Exeter stem. RESULTS: The mean postoperative follow-up period was 13.3 years. Femoral-side revision was required in 14 hips, with no cases of aseptic stem loosening-associated revision observed. Kaplan-Meier survival analysis predicted 97.3% 15-year survival when revision for any reason was used as the endpoint. CONCLUSION: The obtained findings suggested the excellent long-term stability of the Exeter stem for primary total hip arthroplasty in Japan.

Impaction bone grafting for femoral revision hip arthroplasty with Exeter stem in Japan: An extended 10- to 15-year stem survival analysis of the previously reported series.

BACKGROUND: Femoral impaction bone grafting (IBG) was introduced in the late 1990s in Japan and has gradually become recognized as a useful option for femoral revision. The aim of the present study was to retrospectively analyze 10 to 15 years of clinical results of femoral revision arthroplasties of IBG using Exeter stem performed by experienced Japanese surgeons. METHODS: We investigated radiographic and clinical records more than 2 years after surgery in 99 hips of 93 patients. The average age was 66.3 years (36-84 years) and the average follow-up period was 11 years (2-23 years and 8 months). Merle d'Aubigné and Postel hip score was used for clinical assessment, and re-operations for any reason were recorded. The survival curve was estimated using Kaplan-Meier method. RESULTS: The mean Merle d'Aubigné and Postel hip score improved from 9.0 points to 14.5 points at the final follow-up. Re-operations were undertaken in 15 hips of 14 patients for aseptic acetabular component loosening (n = 1 hip), recurrent dislocation (n = 2 hips), infection (n = 4 hips), and periprosthetic femoral fracture (n = 8 hips). The survival rates at 10 and 15 years after operation were 87.1% and 81.1% with any type of re-operation as the endpoint, 92.2% and 92.2% with stem removal or exchange as the endpoint, 94.9% and 88.1% with re-operation for periprosthetic femoral fracture as the endpoint, and 99.0% and 99.0% with re-operation for aseptic stem loosening as the endpoint, respectively. CONCLUSIONS: The present study showed encouraging results of femoral IBG over 10 years by experienced surgeons in Japan. Although femoral IBG is recognized as a technically complex procedure, survivorship of the stem is excellent, with a 15-year stem survival rate of 99.0% at the end point of aseptic loosening.

Superconductivity in High-Entropy Antimonide M1-xPtxSb (M = Equimolar Ru, Rh, Pd, and Ir).

The high-entropy concept was applied to the synthesis of transition-metal antimonides, M1-xPtxSb (M = equimolar Ru, Rh, Pd, and Ir). High-entropy antimonide samples crystallized in a pseudo-hexagonal NiAs-type crystal structure with a P63/mmc space group were successfully synthesized through a conventional solid-state reaction and subsequent quenching. A detailed investigation of the composition and equilibration conditions confirmed the reversible phase transition between a multiphase state at low temperature and an entropy-driven single-phase solid solution at high temperatures. Electrical resistivity, magnetization, and heat capacity measurements of single-phase M1-xPtxSb (x = 0.2) samples revealed a bulk superconducting transition at 2.15(2) K. This study demonstrates that the high-entropy concept provides numerous opportunities for the discovery of new functional materials such as superconductors.

Overestimation of fibrinogen concentration in cryoprecipitate by repeated freeze-thawing with long thawing period as used in the Clauss method.

BACKGROUND: Cryoprecipitate (CRY) is widely used for treating acquired hypofibrinogenemia. During our study to determine an optimal preparation method, we noticed that the measurement of fibrinogen concentration in CRY had a risk of overestimation. We analyzed this condition and mechanism. STUDY DESIGN AND METHODS: CRY was prepared from fresh frozen plasma (FFP) under four conditions: A, 30 h thawing time, 2 cycles; B, 24 h thawing time, 2 cycles; C, 30 h thawing time, 1 cycle; and D, 24 h thawing time, 1 cycle. Then, fibrinogen concentrations in CRY and cryosupernatant (CS) were measured by the Clauss method. RESULTS: Purification (CRY/CRY+CS) and recovery (CRY/FFP) rates in CRY prepared under 2-cycle conditions were higher than those under 1 cycle. However, recovery rates often exceeded 100%, particularly in the case of CRY prepared under A condition, and fibrinogen concentrations calculated by direct measurement were higher than those indirectly calculated from FFP and CS, suggesting an overestimation of fibrinogen values. The level of soluble fibrin monomer complex was considerably higher in CRY prepared under A than under D condition, indicating that CRY adopted a hypercoagulated state. We further found that repeated thawing/freezing increased fibrinogen values as measured by the Clauss method while mechanical vortexing did not. DISCUSSION: Our findings suggest that direct assessment of fibrinogen contents in CRY prepared by repeated freeze-thawing with a longer thawing period presents a higher risk of overestimation. For the purpose of quality control, we propose an alternative method to indirectly estimate fibrinogen concentrations in CRY from those of CS and FFP.

Fermi surface and light quasi particles in hourglass nodal chain metalß-ReO2.

Quantum oscillations (QOs) in magnetic torque and electrical resistivity were measured to investigate the electronic structure ofß-ReO2, a candidate hourglass nodal chain (NC) metal (Dirac loop chain metal). All the de Haas-van Alphen oscillation branches measured at 30 mK in magnetic fields of up to 17.5 T were consistent with first-principles calculations predicting four Fermi surfaces (FSs). The small-electron FS of the four FSs exhibited a very small cyclotron mass, 0.059 times that of the free electrons, which is likely related to the linear dispersion of the energy band. The consistency between the QO results and band calculations indicates the presence of the hourglass NC predicted forß-ReO2in the vicinity of the Fermi energy.

Mean 14-year Outcomes of Hybrid Total Hip Arthroplasty Using Bulk Femoral Head Autografts for Acetabular Reconstruction.

BACKGROUND: We aimed to evaluate the mean 14-year outcomes of hybrid total hip arthroplasty (THA) with cementless acetabular cups using bulk femoral head autografts in acetabular reconstruction and specify the radiological characteristics of cementless acetabular cups using this technique. METHODS: This retrospective study included 98 patients (123 hips) who underwent hybrid THA with a cementless acetabular cup using bulk femoral head autografts for bone deficiency in acetabular dysplasia and who were followed-up for a mean of 14 years (range, 10 to 19.6). The percentage of bone coverage index (BCI) and cup center-edge (CE) angles were evaluation radiologically of acetabular host bone coverage. The survival rate of the cementless acetabular cup and autograft bone ingrowth were assessed. RESULTS: The survival rate with all revisions of cementless acetabular cups was 97.1% (95% confidence interval: 91.2 to 99.1). The autograft bone was remodeled or reoriented in all cases except in 2 hips where the bulk femoral head autograft collapsed. Radiological evaluation revealed a mean cup CE angle of -17.8° (range, -52 to -7°) and a BCI of 44.4% (range, 10 to 75.4%). CONCLUSION: Cementless acetabular cups using bulk femoral head autografts for bone deficiency of the acetabular roof remained stable even if the average BCI was 44.4% and the average cup CE angle was -17.8°. Cementless acetabular cups using these techniques showed good 10-year to 19.6-year outcomes and viabilities of graft bones.

Total hip arthroplasty with femoral shortening osteotomy using polished cemented stem vs. modular cementless stem in patients with Crowe type IV developmental dysplasia of the hip.

INTRODUCTION: There is still little information regarding the advantages of a using a polished tapered stem for Crowe Type IV developmental dysplasia of the hip (DDH). This study aimed to investigate the mid-term clinical and radiological outcomes of primary total hip arthroplasty (THA) with femoral shortening osteotomy using modular and polished tapered stems and to compare the results between the modular and polished tapered stems. MATERIALS AND METHODS: This retrospective review included 32 patients (37 hips) with Crowe type IV DDH who underwent primary THA with femoral shortening osteotomy using a modular stem (cementless group, 14 hips) or a polished tapered stem (cement group, 23 hips) between 1996 and 2018. Clinical data and radiographic assessments were reviewed to analyze the differences between the two groups. RESULTS: The mean duration of patient follow-up of the cementless group (134.4 months) was longer than that of the cement group (75.5 months). There were no differences in clinical results, time of bone union, and survival rate between the two groups. However, the cementless group exhibited a higher ratio of intraoperative fracture and thinning of cortical bone including stress shielding, medullary changes, stem alignment changes, and osteolysis, compared to the cement group. CONCLUSIONS: The findings of this study suggest that THA with femoral shortening osteotomy using both cemented and modular stems can provide satisfactory results. However, considering the occurrence of intraoperative fracture and radiographic analysis in the current study, the cement stem may have an advantage for patients with bone fragility and deterioration in bone quality.

Cilia-Mediated Insulin/Akt and ST2/JNK Signaling Pathways Regulate the Recovery of Muscle Injury.

Following injury, skeletal muscle regenerates but fatty tissue accumulation is seen in aged muscle or muscular dystrophies. Fibro/adipogenic progenitors (FAPs) are key players in these events; however, the effect of primary cilia on FAPs remains unclear. Here, it is reported that genetic ablation of trichoplein (TCHP), a ciliary regulator, induces ciliary elongation on FAPs after injury, which promotes muscle regeneration while inhibiting adipogenesis. The defective adipogenic differentiation of FAPs is attributed to dysfunction of cilia-dependent lipid raft dynamics, which is critical for insulin/Akt signaling. It is also found that interleukin (IL) 13 is substantially produced by intramuscular FAPs, which are upregulated by ciliary elongation and contribute to regeneration. Mechanistically, upon injury, long cilia excessively activate the IL33/ST2/JNK axis to enhance IL13 production, facilitating myoblast proliferation and M2 macrophage polarization. The results indicate that FAPs organize the regenerative responses to skeletal muscle injury via cilia-mediated insulin/Akt and ST2/JNK signaling pathways.

Linear Trimer Molecule Formation by Three-Center-Four-Electron Bonding in a Crystalline Solid RuP.

Some inorganic solids undergo phase transitions that result in the formation of "molecules" in their crystalline frameworks, which are frequently accompanied by dramatic changes in physical properties; the metal-insulator transition (MIT) in vanadium dioxide, for instance, is accompanied by the formation of dimer molecules with conventional two-center-two-electron bonding. We have discovered the creation of a linear ruthenium trimer with atypical three-center-four-electron bonding in ruthenium monophosphide at its MIT. Our detailed structural investigation and electronic structure calculations reveal that charge transfer from polymerized phosphorous to ruthenium automatically tunes the electron density to precisely four per trimer at the MIT, with all conduction electrons present at high temperatures being trapped by the trimer's molecular orbitals at low temperatures. Our results demonstrate that molecules are essential even in solid crystals, as they impact their electronic properties.

A bifurcation concept for B-lymphoid/plasmacytoid dendritic cells with largely fluctuating transcriptome dynamics.

Hematopoiesis was considered a hierarchical stepwise process but was revised to a continuous process following single-cell RNA sequencing. However, the uncertainty or fluctuation of single-cell transcriptome dynamics during differentiation was not considered, and the dendritic cell (DC) pathway in the lymphoid context remains unclear. Here, we identify human B-plasmacytoid DC (pDC) bifurcation as large fluctuating transcriptome dynamics in the putative B/NK progenitor region by dry and wet methods. By converting splicing kinetics into diffusion dynamics in a deep generative model, our original computational methodology reveals strong fluctuation at B/pDC bifurcation in IL-7Rα+ regions, and LFA-1 fluctuates positively in the pDC direction at the bifurcation. These expectancies are validated by the presence of B/pDC progenitors in the IL-7Rα+ fraction and preferential expression of LFA-1 in pDC-biased progenitors with a niche-like culture system. We provide a model of fluctuation-based differentiation, which reconciles continuous and discrete models and is applicable to other developmental systems.

Long-term outcomes and central nervous system relapse in extranodal natural killer/T-cell lymphoma.

To elucidate the long-term outcomes of non-anthracycline-containing therapies and central nervous system (CNS) events in patients with extranodal NK/T-cell lymphoma, nasal type (ENKTL), the clinical data of 313 patients with ENKTL diagnosed between 2000 and 2013 in a nationwide retrospective study in Japan were updated and analyzed. At a median follow-up of 8.4 years, the 5-year overall survival (OS) and progression-free survival (PFS) were 71% and 64%, respectively, in 140 localized ENKTL patients who received radiotherapy-dexamethasone, etoposide, ifosfamide, and carboplatin (RT-DeVIC) in clinical practice. Nine (6.4%) patients experienced second malignancies. In 155 localized ENKTL patients treated with RT-DeVIC, 10 (6.5%) experienced CNS relapse (median, 12.8 months after diagnosis). In five of them, the events were confined to the CNS. Nine of the 10 patients who experienced CNS relapse died within 1 year after CNS relapse. Multivariate analysis identified gingival (hazard ratio [HR], 54.35; 95% confidence interval [CI], 8.60-343.35) and paranasal involvement (HR, 7.42; 95% CI, 1.78-30.89) as independent risk factors for CNS relapse. In 80 advanced ENKTL patients, 18 received steroid (dexamethasone), methotrexate, ifosfamide, L-asparaginase, and etoposide (SMILE) chemotherapy as first-line treatment. Patients who received SMILE as their first-line treatment tended to have better OS than those who did not (p = 0.071). Six (7.5%) advanced ENKTL patients experienced isolated CNS relapse (median, 2.6 months after diagnosis) and died within 4 months of relapse. No second malignancies were documented in advanced ENKTL patients. In the entire cohort, the median OS after first relapse or progression was 4.6 months. 12 patients who survived 5 years after PFS events were disease-free at the last follow-up. Of those, 11 (92%) underwent hematopoietic stem cell transplantation. Our 8-year follow-up revealed the long-term efficacy and safety of RT-DeVIC and SMILE. The risk of CNS relapse is an important consideration in advanced ENKTL.

Multi-centre study of cement-in-cement and in-cement femoral revision total hip arthroplasty using polished, stainless steel stems.

BACKGROUND: Exposure of the acetabular component during revision total hip arthroplasty is often difficult and stems are often difficult to remove. Polished and tapered cemented stems are easily removed and can be easily reconstructed by either cement-in-cement or in-cement technique. This study was a retrospective review of the medium-term outcomes of revision total hip arthroplasty conducted with the Exeter stem fixed by cement-in-cement or in-cement method in four institutions. METHODS: This study included hips (n = 103) reconstructed by cement-in-cement or in-cement technique on the femoral side during revision total hip arthroplasty in four institutions between 2003 and 2015. The mean age at surgery was 71.1 years (range, 43-86 years), and the mean follow-up period was 5.6 years (range, 0-13 years). RESULTS: Revision arthroplasty was required for acetabular component complications in 69 hips, for dislocation in 25, for infection in eight, and for stem fracture in one hip. Re-revision was required in 10 hips for: infection (n = 6), acetabular component complications (n = 3), and dislocation (n = 1). No radiographic loosening, cement fractures, or osteolysis of the femoral components were observed. Ten-year survival rate was 99% with the endpoint of femoral revision surgery, and 100% with the endpoint of femoral aseptic loosening. CONCLUSIONS: The medium-term outcomes of revision total hip arthroplasty on the femoral side conducted using the cement-in-cement or in-cement technique were favourable, with no cases of aseptic loosening. As long as the bone-cement interface remains robust, there is no need to remove all the cement, and the cement-in-cement or in-cement technique should be used for reconstruction.

Clinical utility of oral management in allogeneic hematopoietic stem cell transplantation recipients: microbiological evidence based on molecular analysis of oral bacteria.

PURPOSE: This study aimed to clarify the clinical utility of oral management to prevent bloodstream infections by oral bacteria microbiologically in patients undergoing allogeneic hematopoietic stem cell transplantation (ASCT). METHODS: Ten consecutive patients with hematological malignancies undergoing ASCT were enrolled in this study. We implemented dental treatments before transplantation, if required, and carried out oral hygiene instructions and oral management every other day after transplantation. Molecular analysis of bacterial DNA for seven oral species using a polymerase chain reaction (PCR) assay was performed for oral samples and peripheral blood once a week for 3 weeks after transplantation. RESULTS: Periodontitis was found in all 10 patients (mild grade in 3 and middle grade in 7) for whom basic periodontal therapy was conducted. Necessary dental procedures, including tooth extraction were performed in 5 patients. After transplantation, oral mucositis occurred in 10 patients (grade 1 in 3, grade 2 in 2, and grade 3 in 5) for whom oral hygiene instruction and oral care were continued every other day. PCR-identified three to six bacterial species in oral samples from nine patients, but none in peripheral blood from any patient during the observation period. CONCLUSIONS: Our study suggests that oral management could prevent bloodstream infections by oral bacteria in ASCT recipients despite the existence of periodontitis or oral mucositis. Its utility was confirmed by microbiological evidence based on molecular data.

Irbesartan, an angiotensin II type 1 receptor blocker, inhibits colitis-associated tumourigenesis by blocking the MCP-1/CCR2 pathway.

The introduction of anti-inflammatory therapies has enabled substantial improvement of disease activity in patients with inflammatory bowel diseases (IBD). However, IBD can lead to serious complications such as intestinal fibrosis and colorectal cancer. Therefore, novel therapies reducing the development of these complications are needed. Angiotensin II (Ang II) promotes tissue inflammation by stimulating the production of monocyte chemoattractant protein-1 (MCP-1) or proinflammatory cytokines. It plays a pivotal role in IBD progression. Although blockade of Ang II has been reported to ameliorate experimental colitis and reduce colorectal cancer risk, the cellular and molecular mechanisms remain poorly understood. Our previous work showed that irbesartan, an Ang II type 1 receptor blocker, reduced the number of C-C chemokine receptor 2-positive (CCR2+) monocytic cells in the inflamed pancreas. This study aimed to investigate the possible antifibrotic and antitumour effects of irbesartan using the azoxymethane/dextran sodium sulphate mouse model. Irbesartan suppressed MCP-1 production and the accumulation of Ly6C+CCR2+ monocytes and fibrocytes in the inflamed colon, downregulated the expression of type 1 collagen and matrix metalloproteinase 9 and inhibited the development of intestinal fibrosis and tumours. Our observations suggest that blocking the MCP-1/CCR2 pathway using irbesartan might be beneficial in preventing colitis-associated colon tumours.

MPL exon 10 mutations other than canonical MPL W515L/K mutations identified by in-house MPL exon 10 direct sequencing in essential thrombocythemia.

MPL exon 10 mutations are one of the driver mutations in essential thrombocythemia (ET) or myelofibrosis (MF). We have established an in-house MPL mutation analysis system, covering the entire region of MPL exon 10 by direct sequencing. Since 2009, MPL exon 10 mutation analysis has been performed for diagnosis of myeloproliferative neoplasms (MPN) without JAK2 V617F or CALR exon 9 mutations. So far, 11 cases of MPL exon 10 mutation have been found in 51 patients with suspected MPN. In patients with ET, we detected five non-canonical MPL mutations including one novel mutation, MPL R514_P518delinsK, and one canonical MPL W515L mutation. Notably, three ET patients without canonical MPL mutations had thrombotic events. Meanwhile, in primary or secondary MF, only canonical MPL W515L/K mutations were found. Further cases need to be examined to elucidate the full MPL mutation profile in MPN. However, our data indicate that analysis of the whole of MPL exon 10 is warranted for the diagnosis of MPL mutations, especially in ET, and that the use of Japanese commercial laboratory tests that only detect canonical MPL W515L/K mutations may miss a significant percentage of MPL exon 10 mutations, which could delay the administration of anti-thrombotic therapy.