Probing Structural Defects in MOFs Using Water Stability.

Defects in the crystal structures of metal-organic frameworks (MOFs), whether present intrinsically or introduced via so-called defect engineering, can play strong roles in the properties of MOFs for various applications. Unfortunately, direct experimental detection and characterization of defects in MOFs are very challenging. We show that in many cases, the differences between experimentally observed and computationally predicted water stabilities of MOFs can be used to deduce information on the presence of point defects in real materials. Most computational studies of MOFs consider these materials to be defect-free, and in many cases, the resulting structures are predicted to be hydrophobic. Systematic experimental studies, however, have shown that many MOFs are hydrophilic. We show that the existence of chemically plausible point defects can often account for this discrepancy and use this observation in combination with detailed molecular simulations to assess the impact of local defects and flexibility in a variety of MOFs for which defects had not been considered previously.

The Preserved Thickness Ratio of the Femoral Head Contributes to the Collapse Predictor of Osteonecrosis.

OBJECTIVES: The collapse of femoral head is a serious symptom of osteonecrosis of the femoral head (ONFH), resulting in hip pain and deformity. However, it is hardly possible to reestablish the femoral head nonoperatively once the collapse happens. Predicting femoral head collapse is of great value for the prognosis of ONFH. This study aimed to develop a new method to quantify the preserved thickness of femoral head and to assess its diagnostic contribution in predicting femoral head collapse on plain radiographs. METHODS: This was a single-center retrospective study. A total of 101 hips (85 patients) with ARCO stage II from January 2008 to December 2016 were included in this study. The preserved thickness was measured on standard anteroposterior (AP) and frog-leg (FL) radiographs. The anteroposterior view's preserved thickness ratio (APTR) and the frog-leg view's preserved thickness ratio (FPTR) were calculated to show the preserved thickness ratio of the femoral head anteriorly and laterally. Univariate and multivariate logistic regression was performed to determine the risk factors for collapse. Sensitivity, specificity, and cut-off values for APTR and FPTR were determined by the receiver operating characteristic (ROC) curve analysis. Kaplan-Meier (K-M) analysis was applied to determine femoral head survival in ONFH patients. RESULTS: The mean age of the 27 females and 58 males was 38.93 years old. The mean follow-up time was 74.62 (36-124) months in the non-collapse group and 18.66 (3-82) months in the collapse group. Femoral head collapse was observed in 62 hips during the follow-up period. Logistic regression analysis and ROC results showed that APTR <24.79% and FPTR <10.62% were significantly correlated with femoral head collapse. The Kaplan-Meier survival curve suggested that the overall survival rate of APTR ≥24.79% was 68.2% at 5 and 10 years and FPTR ≥10.62% was 71.63% at 5 and 10 years. At the last follow-up, 26 hips had collapse on the anterior side of the femoral head, 12 hips occurred on the lateral side, and 24 hips happened to collapse on both anterior and lateral sides. CONCLUSION: Femoral head collapse predominantly occurred anteriorly rather than laterally in ONFH patients. The measurements of APTR and FPTR have noticeable implications for the prediction of femoral head collapse, and contribute to the selection of treatment options for ONFH patients with types B and C1 according to the JIC classification.

Identification and validation of ferroptosis-related biomarkers in steroid-induced osteonecrosis of the femoral head.

OBJECTIVES: Treatment of steroid-induced osteonecrosis of the femoral head (SIONFH) is challenging. Due to the limited understanding of its molecular mechanisms, investigating the potential mechanisms of ferroptosis will shed light on SIONFH and provide directions for treating this disease. METHODS: The GSE123568 dataset was utilized to apply various bioinformatics methodologies to identify ferroptosis-related hub genes (FRHGs). Subsequently, the importance of these genes and the reliability of the results were confirmed using protein data-independent acquisition (DIA) and cell experiments. Finally, we assessed the correlation between FRHG expression and immune cell infiltration. RESULTS: Thirty-one hub genes were identified and validated by constructing a protein-protein interaction network and subsequent screening using experimentally determined interactions. These 31 hub genes were enriched in immunity, the AMPK signaling pathway, and the Toll-like receptor signaling pathway. Next, we identified a diagnostic marker comprising two ferroptosis-related genes, NCF2 and SLC2A1. The differential expression of these two genes in healthy and necrotic regions was confirmed by protein DIA analysis. Cell experiments verified the link between FRHGs and ferroptosis and preliminarily explored the potential mechanism of the antioxidant vitexin in promoting osteogenic differentiation in cells. The diagnostic efficiency of these two markers was confirmed by receiver operating characteristic curve (ROC) curves, yielding an area under the curve of 1.0. Gene Ontology (GO) and Kyoto Encyclopedia of Genes and Genomes (KEGG) indicated enrichment of FRHGs in the superoxide anion and HIF-1 signaling pathways. A significant correlation was observed between FRHGs and various immune cell populations. CONCLUSION: NCF2 and SLC2A1 are promising ferroptosis-related diagnostic biomarkers of SIONFH. Concurrently, we embarked on a preliminary investigation to elucidate the potential mechanism underlying the promotion of osteogenic differentiation by the antioxidant vitexin. Moreover, these biomarkers are associated with distinct immune cell populations.

Meta-analysis of effectiveness and safety of glucocorticoid combined with hydroxychloroquine in the treatment of systemic lupus erythematosus rash.

BACKGROUND: Many studies have found that glucocorticoid (GC) combined with hydroxychloroquine (HCQ) has a good clinical effect in the treatment of systemic lupus erythematosus (SLE) rash, but there is no relevant systematic evaluation at present. The purpose of this study was to systematically evaluate and analyze the effectiveness and safety of GC combined with HCQ in the treatment of SLE rash. METHODS: Randomized controlled trials of GC combined with HCQ in the treatment of SLE rash were collected through computer retrieval of Cochrane Library, PubMed, Embase, CNKI, China Science and Technology Journal Database (VIP), Wanfang Data Knowledge Service Platform (Wanfang), and China Biology Medicine disc (CBM) since the establishment of the database. The main outcome indicators included clinical total effective rate, adverse reactions, SLE disease activity index (SLEDAI) score, erythrocyte sedimentation rate (ESR), C-reactive protein (CRP), and complement 3 (C3). A meta-analysis was conducted using Review Manager 5.3 software. RESULTS: A total of 11 studies involving 809 patients (406 in the test group and 403 in the control group) were included in this article. The meta-analysis results showed that compared with the single use of GC, GC combined with HCQ could improve the clinical total effective rate in the treatment of SLE rash (odds ratio [OR] = 4.27, 95% confidence interval [CI] 2.50-7.30, p < .00001), and reduce the occurrence of adverse reactions (OR = 0.26, 95% CI 0.15-0.44, p < .00001); effectively reduce SLEDAI score (mean difference [MD] = 1.88, 95% CI 1.66-2.10, p < .00001) and ESR level (MD = 7.92, 95% CI 5.66-10.19, p < .00001); increase C3 level after treatment (MD = 0.36, 95% CI 0.32-0.41, p < .00001); and reduce CRP level (MD = 3.22, 95% CI 2.87-3.58, p < .00001), with statistically significant differences. CONCLUSION: Compared with the use of GC alone, GC combined with HCQ can improve the clinical effectiveness of SLE rash treatment, with a low incidence of adverse reactions and good clinical safety. However, the number and quality of studies included in this article were not high, so the findings need to be further verified by high-quality, multicenter randomized controlled trials.

Evaluation of the predictive values of collapse and necrotic lesion boundary for osteonecrosis of the femoral head prognosis.

Objective: Osteonecrosis of the femoral head (ONFH) is a disabling and intractable orthopedic disease largely affecting young and middle-aged groups. Current standard of treatment relies on the collapse of femoral head as a predictor for prognosis. However, a wide range of variability in repair potentials is observed in patients with femoral head collapse. Therefore, the present study aimed to evaluate the accuracy of femoral head collapse as a predictor and to propose the necrotic lesion boundary as a novel yet reliable measure for ONFH prognosis. Methods: A retrospective cross-sectional study was conducted at the First Affiliated Hospital of Guangzhou University of Chinese Medicine, 203 hips with ONFH from 134 patients were included. The occurrences and progression of femoral head collapse were recorded. Necrosis lesion boundary was quantified and classified for each case based on anteroposterior view intact ratio (APIR) and the frog-leg view intact ratio (FLIR) as independent variables. Dependent variables were defined as progressive collapse or terminal collapse for Association Research Circulation Osseous (ARCO) stage II and III respectively. Logistic regression analysis, Receiver Operating Characteristic (ROC) curve and Kaplan-Meier (K-M) survival analysis was performed and results were interpreted. Results: Out of the 106 hips in ARCO stage II, 31 hips collapsed with further progression, while 75 hips had no collapse or collapse with repair of the necrotic areas. Out of the 97 hips in ARCO stage IIIA, the collapse continued to progress in 58 hips while the necrotic areas were repaired in 39 hips. Logistic regression analysis demonstrated that both APIR and FLIR, were independent risk factors. Further ROC curve analysis indicated that the cutoff values of APIR and FLIR could be considered as indications for evaluating the prognosis of ONFH. Contrary to the traditional view of poor prognosis after femoral head collapse, K-M survival analysis demonstrated a high value of APIR and FLIR for ONFH prognosis. Conclusion: The present study found that the occurrence of collapse is an oversimplified predictor for ONFH prognosis. The collapse of the femoral head in ONFH does not predict a poor prognosis. The necrosis lesion boundary has a high value in predicting ONFH prognosis and informing clinical treatment strategies.

Multidisciplinary treatment of giant presacral solitary fibrous tumour: a case report and literature review.

Solitary fibrous tumours (SFTs) usually occur at the pleura. Extrapleural sites, particularly giant extrapleural solitary fibromas, are more rarely observed in the clinic, and the clinical diagnosis and treatment of this disease is a focus of attention. Herein, the case of a 43-year-old male patient with giant presacral SFT successfully treated by open surgery, and with a final diagnosis confirmed by postoperative pathology and immunohistochemistry, is reported. The patient was followed-up regularly during 5 years after surgery, with no obvious surgical complications, and no tumour recurrence noted on pelvic magnetic resonance imaging. This case provides clinical information that may help in the diagnosis and treatment of complex SFT.

Loureirin B downregulates osteoclast differentiation of bone marrow macrophages by targeting the MAPK signaling pathway.

Excessive absorption of osteoclasts will break the balance between osteoclasts and osteoblasts, leading to bone loss, decreased bone density, and increased bone fragility. We have shown that Loureirin B (LrB) can inhibit osteoclasts. In this study, we demonstrated the targeting-inhibitory mechanism of LrB acting on osteoclast precursor. Using SPR, HPLC and MALDI-TOF-MS to capture and analyze the target protein of Loureirin B in bone marrow macrophages (BMMs), we used this method to detect all target proteins that LrB acts on BMMs, and analyzed the distribution and enrichment rate of the target protein by DAVID enrichment analysis. Ledock molecular docking was used to detect the binding of LrB. We used Western Blot for verification. The target proteins of LrB acting on BMMs were Serpine1, Atp6ap1, Dvl1, Rhd, Fzd2, MAPK1, MAP2K2, MAPK3 and so on. MAPK1, MAP2K2 and MAPK3 were the most relevant. LrB treatment attenuated the expression of phosphorylated JNK and p38 kinases of the MAPK signaling pathway. Our research further confirmed that LrB affects the MAPK signaling pathway in BMMs, thereby inhibiting the differentiation of BMMs into osteoclasts. This discovery can confirm the mechanism by which LrB acts on BMMs.

Clinical Outcome of Surgical Hip Dislocation Combined with Impacting Bone Grafts and Implanting Iliac Bone Flaps in the Treatment of Osteonecrosis of the Femoral Head: A Mid-term Retrospective Study.

OBJECTIVE: To report the medium-term outcomes of surgical hip dislocation (SHD) combined with impacting bone grafts and implanting iliac bone flaps in the treatment of osteonecrosis of the femoral head (ONFH) and to define the indications for this treatment. METHODS: This was a single-center retrospective study. In total, 64 patients (70 hips) with ONFH treated from January 2014 to December 2017 were included in this study. There were 51 males and 13 females aged 18-55 years with an average age of 32 years. All patients underwent surgery for SHD combined with impacting bone grafts and implanting iliac bone flaps. Preoperative and postoperative clinical outcomes were assessed. The clinical outcome was assessed using the Harris hip score (HHS) and the conversion rate of total hip arthroplasty (THA). Univariate and multivariate logistic regression analyses were performed to identify risk factors affecting the clinical outcome. Kaplan-Meier (K-M) analysis was applied to calculate the survival rate of the femoral head. RESULTS: At the last follow-up (60 ± 15.08 months), the HHS was excellent for 41 hips, good for 17 hips, fair for three hips, and poor for nine hips. All nine hips with poor HHS underwent THA, including five in the first 2 years following the index surgery and four between three and 5 years. The conversion rate of total hip arthroplasty was 12.86%. Univariate and multivariate logistic regression analyses showed that the duration of hip pain and JIC classification type were significantly associated with clinical outcomes. Elderly age and advanced ONFH stage tended to lead to worse surgical outcomes. The overall survival rate of JIC classification type C1 and duration of pain ≤6 months was 98.1% and 97.8% at 72 months, respectively, as estimated by the Kaplan-Meier method. CONCLUSION: Surgical hip dislocation combined with impacting bone grafts and implanting iliac bone flaps in the treatment of ONFH had a good mid-term clinical outcome, especially for patients with retention of the lateral column of the femoral head and hip pain less than 1 year.

Diagnostic value of necrotic lesion boundary in bone collapse of femoral head osteonecrosis.

PURPOSE: Our research developed a novel approach to quantitatively evaluate the boundary of necrotic lesions in osteonecrosis of the femoral head (ONFH) and to explore its diagnostic value in predicting bone collapse of the femoral head. METHODS: A retrospective cross-sectional study was conducted in our institution, and 146 hips (121 cases) identified as ONFH were recruited. The anterior and lateral boundaries of each enrolled subject were measured in standard anteroposterior (AP) view and frog-leg (FL) view of plain radiographic images, the intact rate of which was then calculated and presented as the anteroposterior view intact ratio (APIR) and frog-leg view intact ratio (FLIR), respectively. Univariate and multivariate logistic regression analyses were performed to identify risk factors for collapse. A receiver operating characteristic (ROC) curve analysis was performed to determine the sensitivity, specificity and cutoff value of the APIR and FLIR. A Kaplan-Meier (K-M) analysis was applied to calculate the survival rate of the femoral head, and bone collapse of the femoral head was regarded as the endpoint. RESULTS: Femoral head collapse was observed in 61 hips during the follow-up period. Patients with or without femoral head collapse were categorized into the collapse group and non-collapse group, respectively. The mean follow-up time was 3.7 years (2-9) for the collapse group and 7.7 years (5-20) for the non-collapse group. Univariate and multivariate logistic regression analysis and ROC analysis showed that APIR (< 25.61%) and FLIR (< 24.43%) were significantly associated with femoral head collapse. The K-M survival curves indicated that the overall survival rate of APIR (≥ 25.61%) was 94.8% at 7.5 years and 76.6% at 10 years, while that of FLIR (≥ 24.43%) was 87.3% at 7.5 years and ten years. CONCLUSION: The present study demonstrates that APIR and FLIR are of high diagnostic value in the early and middle stages of ONFH. APIR and FLIR can be used to predict the occurrence of femoral head collapse in patients with JIC classification types B and C1. The measurement of these two parameters in plain radiography images may contribute to the selection of a proper hip preservation strategy.

The association the patient-reported outcomes after periacetabular osteotomy with radiographic features: a short-term retrospective study.

BACKGROUND: Bernese periacetabular osteotomy (PAO) is an effective treatment for patients with developmental dysplasia of the hip (DDH). PAO has been widely used in China, but few follow-up outcomes have been reported in the international community. Moreover, the risk factors affecting patient-reported outcomes have not been discussed in recent studies. In this study, patient-reported outcomes after PAO were reported, and risk factors affecting patient-reported outcomes were analyzed. METHODS: Patients who underwent PAO for DDH from January 2014 to January 2020 were selected as the study subjects, and 66 hips were included in the analysis after screening (59 patients, with an average follow-up time of 3.01 years). The Harris Hip Score (HHS) and International Hip Outcome Instrument-12 (iHOT-12) were used to assess hip function and patient quality of life. The changes of preoperative and latest follow-up HHSs less than 9 were defined as symptomatic hips, that is, an adverse outcome; otherwise, the score indicates preserved hips. Also, the changes of preoperative and latest follow-up iHOT-12 were defined as symptomatic hips and preserved hips. Multivariate logistic regression analysis was used to predict the risk factors influencing the patient-reported outcomes, and receiver operating characteristic (ROC) curve analysis was performed on the risk factors to determine their sensitivity, specificity and cutoff value. RESULTS: Clinical outcome analysis demonstrates marked improvements in patient-reported outcomes. The multivariate logistic regression analysis showed that when the postoperative LCEA was > 38°, adverse outcomes were much more likely. However, a Tönnis angle of - 10° to 0° was a protective factor. In addition, hips with fair or poor joint congruency were more likely to develop negative outcomes. The ROC curve analysis showed that the optimal thresholds for the LCEA and Tönnis angles used to predict outcomes after PAO were 38.2° and - 9°, respectively. Based on the results of the ROC curve analysis, among hips with poor or fair joint congruency preoperatively treated by surgeons who obtained the improper postoperative LCEAs and Tönnis angles, bad patient-reported outcomes will most likely be obtained. CONCLUSIONS: Our results demonstrate marked improvements in patient-reported outcomes. Among hips with preoperative excellent or good joint congruency treated by experienced surgeons who obtain the proper postoperative LCEA and Tönnis angles, good patient-reported outcomes can be expected.

A Strong Test of Atomically Detailed Models of Molecular Adsorption in Zeolites Using Multilaboratory Experimental Data for CO2 Adsorption in Ammonium ZSM-5.

A recent international interlaboratory study led by the U.S. National Institute of Standards (NIST) reported CO2 adsorption isotherms measured independently by 11 groups on reference material RM 8852, an ammonium ZSM-5 zeolite. Good reproducibility and high reliability of this experimental data provide a strong test for the ability of atomically detailed models to predict adsorption of CO2 in zeolites. We developed force fields for CO2 in ammonium zeolites based on first-principles calculations and also independently performed experiments with RM 8852 by microcalorimetry. At low pressures good agreement was obtained between predictions and experiments. At high pressures, however, deviations were observed. We show that the charge-balancing cations in the experimental material are the predominant source of the discrepancy between simulation and experiment at high pressures; the experimental sample treatment causes deammoniation. In addition, accounting for a small amount of noncrystalline mesoporosity in the zeolite brings predictions into much better agreement with experiments.

First principles derived, transferable force fields for CO2 adsorption in Na-exchanged cationic zeolites.

The development of accurate force fields is vital for predicting adsorption in porous materials. Previously, we introduced a first principles-based transferable force field for CO2 adsorption in siliceous zeolites (Fang et al., J. Phys. Chem. C, 2012, 116, 10692). In this study, we extend our approach to CO2 adsorption in cationic zeolites which possess more complex structures. Na-exchanged zeolites are chosen for demonstrating the approach. These methods account for several structural complexities including Al distribution, cation positions and cation mobility, all of which are important for predicting adsorption. The simulation results are validated with high-resolution experimental measurements of isotherms and microcalorimetric heats of adsorption on well-characterized materials. The choice of first-principles method has a significant influence on the ability of force fields to accurately describe CO2-zeolite interactions. The PBE-D2 derived force field, which performed well for CO2 adsorption in siliceous zeolites, does not do so for Na-exchanged zeolites; the PBE-D2 method overestimates CO2 adsorption energies on multi-cation sites that are common in cationic zeolites with low Si/Al ratios. In contrast, a force field derived from the DFT/CC method performed well. Agreement was obtained between simulation and experiment not only for LTA-4A on which the force field fitting is based, but for other two common adsorbents, NaX and NaY.

Extra-framework aluminium species in hydrated faujasite zeolite as investigated by two-dimensional solid-state NMR spectroscopy and theoretical calculations.

Extra-framework aluminium (EFAL) species in hydrated dealuminated HY zeolite were thoroughly investigated by various two-dimensional solid-state NMR techniques as well as density functional theoretical calculations. (27)Al MQ MAS NMR experiments demonstrated that five-coordinated and four-coordinated extra-framework aluminium subsequently disappeared with the increase of water loading, and the quadrupole interaction of each aluminium species decreased gradually during the hydration process. (1)H double quantum MAS NMR revealed that the EFAL species in the hydrated zeolite consisted of three components: a hydroxyl AlOH group, and two types of water molecule (rigid and mobile water). (1)H-(27)Al LG-CP HETCOR experiments indicated that both the extra-framework and the framework Al atoms were in close proximity to the rigid water in the fully rehydrated zeolite. The experimental results were further confirmed by DFT theoretical calculations. Moreover, theoretical calculation results further demonstrated that the EFAL species in the hydrated zeolite consisted of the three components and the calculated (1)H NMR chemical shift for each component agreed well with our NMR observations. It is the rigid water that connects the extra-framework aluminium with the four-coordinated framework aluminium through strong hydrogen bonds.