Smoking and osteoimmunology: Understanding the interplay between bone metabolism and immune homeostasis.

Smoking continues to pose a global threat to morbidity and mortality in populations. The detrimental impact of smoking on health and disease includes bone destruction and immune disruption in various diseases. Osteoimmunology, which explores the communication between bone metabolism and immune homeostasis, aims to reveal the interaction between the osteoimmune systems in disease development. Smoking impairs the differentiation of mesenchymal stem cells and osteoblasts in bone formation while promoting osteoclast differentiation in bone resorption. Furthermore, smoking stimulates the Th17 response to increase inflammatory and osteoclastogenic cytokines that promote the receptor activator of NF-κB ligand (RANKL) signaling in osteoclasts, thus exacerbating bone destruction in periodontitis and rheumatoid arthritis. The pro-inflammatory role of smoking is also evident in delayed bone fracture healing and osteoarthritis development. The osteoimmunological therapies are promising in treating periodontitis and rheumatoid arthritis, but further research is still required to block the smoking-induced aggravation in these diseases. Translational potential: This review summarizes the adverse effect of smoking on mesenchymal stem cells, osteoblasts, and osteoclasts and elucidates the smoking-induced exacerbation of periodontitis, rheumatoid arthritis, bone fracture healing, and osteoarthritis from an osteoimmune perspective. We also propose the therapeutic potential of osteoimmunological therapies for bone destruction aggravated by smoking.

The neural representations of valence transformation in indole processing.

Indole is often associated with a sweet and floral odor typical of jasmine flowers at low concentrations and an unpleasant, animal-like odor at high concentrations. However, the mechanism whereby the brain processes this opposite valence of indole is not fully understood yet. In this study, we aimed to investigate the neural mechanisms underlying indole valence encoding in conversion and nonconversion groups using the smelling task to arouse pleasantness. For this purpose, 12 conversion individuals and 15 nonconversion individuals participated in an event-related functional magnetic resonance imaging paradigm with low (low-indole) and high (high-indole) indole concentrations in which valence was manipulated independent of intensity. The results of this experiment showed that neural activity in the right amygdala, orbitofrontal cortex and insula was associated with valence independent of intensity. Furthermore, activation in the right orbitofrontal cortex in response to low-indole was positively associated with subjective pleasantness ratings. Conversely, activation in the right insula and amygdala in response to low-indole was positively correlated with anticipatory hedonic traits. Interestingly, while amygdala activation in response to high-indole also showed a positive correlation with these hedonic traits, such correlation was observed solely with right insula activation in response to high-indole. Additionally, activation in the right amygdala in response to low-indole was positively correlated with consummatory pleasure and hedonic traits. Regarding olfactory function, only activation in the right orbitofrontal cortex in response to high-indole was positively correlated with olfactory identification, whereas activation in the insula in response to low-indole was negatively correlated with the level of self-reported olfactory dysfunction. Based on these findings, valence transformation of indole processing in the right orbitofrontal cortex, insula, and amygdala may be associated with individual hedonic traits and perceptual differences.

Developing a novel strategy for fabricating matrix film to assess the distribution of potassium perfluorooctanic sulfonate by matrix-assisted laser desorption/ionization mass spectrometry imaging.

Matrix deposition plays a critical role in image quality of matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI). To improve the ionization efficiency and overcome the limitation of traditional matrix deposition methods in the face of difficult-to-sublimate or difficult-to-dissolve matrix, covalent organic frameworks (COFs) named COF-DhaTab was successfully synthesized and firstly used as matrix film. It was fabricated by imprinting of sieved COF-DhaTab powder on the surface of a double-sided adhesive tape. Outstanding reproducibility and uniformity of COF-DhaTab film were demonstrated by relative standard deviation (RSD) within 8.37% and 7.71% from dot-to-dot and plate-to-plate, respectively. With the introduction of double-sided adhesive tape, water contact angle (WCA) of COF-DhaTab film increased from 55° to 141°, resulting in significant suppression of analyte diffusion. Moreover, the intensity of potassium perfluorooctanic sulfonate (PFOS, C8F17SO3-, m/z 498.93) was 9.3 × 105, more than six hundred times higher than that using DHB matrix. This enhancement was attributed to the rough surface and multiple branches of the synthesized COF-DhaTab. To verify the ability of COF-DhaTab film as substrate, the spatial distribution of PFOS in zebrafish, rat liver and kidney tissues was explored. Superior imaging capability was displayed with high-spatial resolution and reliable location distribution. These results not only demonstrate the outstanding ability of COF-DhaTab as matrix for MALDI-MS and MALDI-MSI, but also provide a facile approach for fabrication of novel matrix films for MALDI-MSI.

Dipeptidase 1 promotes ferroptosis in renal tubular epithelial cells in diabetic nephropathy via inhibition of the GSH/GPX4 axis.

Renal tubular injury is an important pathological change associated with diabetic nephropathy (DN), in which ferroptosis of renal tubular epithelial cells is critical to its pathogenesis. Inhibition of the glutathione/glutathione peroxidase 4 (GSH/GPX4) axis is the most important mechanism in DN tubular epithelial cell ferroptosis, but the underlying reason for this is unclear. Our biogenic analysis showed that a zinc-dependent metalloproteinase, dipeptidase 1 (DPEP1), is associated with DN ferroptosis. Here, we investigated the role and mechanism of DPEP1 in DN tubular epithelial cell ferroptosis. DPEP1 upregulation was observed in the renal tubular epithelial cells of DN patients and model mice, as well as in HK-2 cells stimulated with high glucose. Furthermore, the level of DPEP1 upregulation was associated with the degree of tubular injury in DN patients and HK-2 cell ferroptosis. Mechanistically, knocking down DPEP1 expression could alleviate the inhibition of GSH/GPX4 axis and reduce HK-2 cell ferroptosis levels in a high glucose environment. HK-2 cells with stable DPEP1 overexpression also showed GSH/GPX4 axis inhibition and ferroptosis, but blocking the GSH/GPX4 axis could mitigate these effects. Additionally, treatment with cilastatin, a DPEP1 inhibitor, could ameliorate GSH/GPX4 axis inhibition and relieve ferroptosis and DN progression in DN mice. These results revealed that DPEP1 can promote ferroptosis in DN renal tubular epithelial cells via inhibition of the GSH/GPX4 axis.

Twice-walk strategy based on three-dimensional DNA walking machine driven by duplex-specific nuclease.

A twice-walk strategy based on a three-dimensional (3D) cleat-equipped DNA walking machine with a high signal amplification efficiency was investigated for ultrasensitive detection of miRNA. Impressively, addition of duplex-specific nuclease (DSN) just once drove the twice-walk strategy, making the strategy simpler. With the advantages of being simple, rapid and ultrasensitive, the biosensor offers potential for use in early clinical diagnosis.

A rapid one-step electrochemical method based on cleat-equipped molecular walking machine.

Various nucleic acid molecular machines have emerged in recent years. However, when the nucleic acid tracks are fully depleted, these walkers are highly susceptible to premature release or stalling in regions where the tracks are locally exhausted. In this work, a molecular walking machine with a cleat domain preventing dissociation from the track was explored for ultrasensitive detection of miRNA. It has been verified that the cleat design can enhance the signal amplification efficiency of molecular walking machines for electrochemical miRNA-141 detection. Notably, the single-step electrochemical biosensing platform utilizing the cleat-equipped molecular walking machine (CMWM) is exceptionally straightforward and rapid, concluding the reaction within 90 min and achieving a remarkable low detection limit of 0.26 fM. The proposed molecular walking machine with this specific cleat structure was utilized for the identification of miRNA-141 in cellular lysates, exhibiting remarkable selectivity and consistent reproducibility, showcasing its effective utility in bioanalysis. Therefore, the cleat walker developed in this study introduces an innovative method for constructing a miRNA electrochemical biosensing platform, offering new perspectives for its application in biomolecule detection and clinical disease diagnosis.

A novel comprehensive strategy for high-thoroughly studying released compounds during the combustion process of herbs. A case study for Artemisia argyi Levl. et Vant.

The comprehensive study of compound variations in released smoke during the combustion process is a great challenge in many scientific fields related to analytical chemistry like traditional Chinese medicine, environment analysis, food analysis, etc. In this work, we propose a new comprehensive strategy for efficiently and high-thoroughly characterizing compounds in the online released complex smokes: (i) A smoke capture device was designed for efficiently collecting chemical constituents to perform gas chromatography-mass spectrometry (GC-MS) based untargeted analysis. (ii) An advanced data analysis tool, AntDAS-GCMS, was used for automatically extracting compounds in the original acquired GC-MS data files. Additionally, a GC-MS data analysis guided instrumental parameter optimizing strategy was proposed for the optimization of parameters in the smoke capture device. The developed strategy was demonstrated by the study of compound variations in the smoke of traditional Chinese medicine, Artemisia argyi Levl. et Vant. The results indicated that more than 590 components showed significant differences among released smokes of various moxa velvet ratios. Finally, about 88 compounds were identified, of which phenolic compounds were the most abundant, followed by aromatics, alkenes, alcohols and furans. In conclusion, we may provide a novel approach to the studies of compounds in online released smoke.

Renomegaly and acute kidney injury as primary manifestations of non-Hodgkin's lymphoma: a report of three cases.

BACKGROUND: In adults with non-Hodgkin's lymphoma, renal enlargement and acute kidney injury occur infrequently at first presentation, especially in T lymphocytic lymphomas. CASE PRESENTATION: We report three cases of non-Hodgkin's lymphoma with acute renal injury and bilateral renal enlargement. At diagnosis, one patient presented with an adrenal mass, one patient's lymph node biopsy was consistent with a renal biopsy, and one patient had primary renal lymphoma with no extrarenal disease. Assessment of renal pathology in Case 2 and Case 3 showed interstitial lymphocyte infiltration; the pathological types were non-Hodgkin's diffuse large B lymphoma originating from activated B cells outside germinal centers and non-Hodgkin's T-lymphoblastic lymphoma/leukemia, respectively. Case 1 did not receive anti-lymphoma therapy and died from infection and multiple organ failure within 1 month of hospitalization. Case 2 received eight courses of R-CHOP; her lymphoma recurred 2 years after diagnosis and she died from severe pulmonary infection 3 years after diagnosis. Case 3 received hyper-CVAD regularly and achieved stable renal function; this patient remains under follow-up. CONCLUSIONS: Renal lymphoma may have diverse manifestations, especially primary renal lymphoma without extrarenal involvement. Nephrologists should pay careful attention to these manifestations to ensure accurate diagnosis.

Preoperative valgus-corrected hip-knee-ankle angle and medial meniscal extrusion are useful for evaluating postoperative alignment in mobile-bearing UKA.

Purpose: The purposes of the study were to analyze the correlation between preoperative variables (valgus corrected hip-knee-ankle angle (vcHKA), medial osteophyte areas of the tibia and femur, and medial meniscus extrusion (MME)) and the postoperative alignment in mobile-bearing unicompartmental knee arthroplasty (UKA). Methods: This study enrolled 109 patients (118 knees) who underwent mobile-bearing UKA between January 1, 2019 and January 1, 2023, retrospectively. Radiographic parameters, including the HKA, hip-knee-shaft angle (HKS), and valgus-corrected femorotibial angle (vcFTA), were measured using preoperative radiographs. The vcHKA was calculated as vcFTA - HKS. The medial osteophyte areas of the tibia and femur and MME were measured using knee magnetic resonance imaging (MRI). Simple and multiple linear regression analyses, univariate and multivariate logistic regression analyses, and receiver operating characteristic (ROC) curves were performed. Results: In total, 109 patients (118 knees) were enrolled in this study. In the multiple linear regression analysis, vcHKA (ß = 0.732, 95 % confidence interval (95%CI) = 0.582 to 0.881; p < 0.001) and MME (ß = 0.203, 95%CI = 0.001 to 0.405; p = 0.049) were positively correlated with postoperative HKA, and postoperative HKA was modeled according to the following equation: 45.420 + (0.732° * vcHKA) + (0.203 mm × MME). In the multivariate logistic regression analysis, vcHKA (odds ratio (OR) = 2.007, 95 % CI = 1.433 to 2.810, p < 0.001) was associated with postoperative valgus malalignment independently. In the ROC curve, vcHKA (cutoff value: 180°) was predictive of postoperative valgus malalignment, with an accuracy (95%CI) of 0.862 (0.780-0.944). Conclusion: Overcorrection of a varus knee under valgus stress radiograph (VSR) and excessive MME on preoperative MRI increase the possibility of overcorrection of postoperative alignment in mobile-bearing UKA.

Pharmacokinetic and pharmacodynamic studies of nicotine in rat brain: a simultaneous investigation of nicotine metabolites and the release of neurotransmitters in vivo.

Introduction: The body's ability to metabolize nicotine and the disposition of nicotine in the brain are important determinants of its exposure. Limited knowledge about the near real-time changes of neurochemicals during the brain nicotine metabolic process hinders the recognition of its multiple neuropharmacological effects. Methods: An online microdialysis coupled with UHPLC-HRMS/MS method for the in vivo multi-analysis of nicotine metabolites and several neurotransmitters in rat brain was developed. Whether the systemic modulation of metabolic enzyme CYP2B would modulate nicotine pharmacokinetics and local neurochemical effects was further investigated. Results: The dynamic profiles of over 10 nicotine metabolites and neurotransmitters were simultaneously obtained after a single injection of nicotine (2 mg·kg-1, i.p.) using the new method. Proadifen pretreatment (50 mg·kg-1·d-1, i.p., 4 days) caused significant inhibition of brain CYP2B1 activity. When exposed to nicotine, the brain C max of nicotine was 1.26 times higher and the levels of nicotine metabolites, nornicotine, and nicotine-N-oxide, were decreased by 85.3% and 34.4% in proadifen-pretreated rats. The higher level of brain nicotine induced a greater release of dopamine, serotonin, glutamate, and γ-amino-butyric acid in the nucleus accumbens. The concentrations of nicotine and dopamine were positively correlated, and the average levels of γ-amino-butyric acid and serotonin were 2.7 and 1.2 times higher, respectively, under the inhibition of nicotine metabolism. Discussion: These results demonstrated that inhibiting nicotine metabolism in rats can enhance the residence of brain nicotine and its local neurotransmitter effects. The metabolic activity of nicotine under different physiological conditions could regulate nicotine's bioavailability and its resulting pharmacology.

Quinoline Bridging Hyperconjugated Covalent Organic Framework as Solid-Phase Microextraction Coating for Ultrasensitive Determination of Phthalate Esters in Water Samples.

Phthalate esters (PAEs) are widely distributed in the environment, and this has caused serious health and safety concerns. Development of rapid and ultrasensitive identification and analysis methods for phthalate esters is urgent and highly desirable. In this work, a novel nitrogen-rich covalent organic framework (N-TTI) derived quinoline bridging covalent organic framework (N-QTTI) was fabricated and used as a solid-phase microextraction (SPME) coating for the ultrasensitive determination of phthalate esters in water samples. The physical and chemical properties of N-QTTI were investigated sufficiently. The N-QTTI-coated fiber demonstrates a superior enrichment performance than either the N-TTI-coated fiber or commercial fibers under the optimized SPME conditions. For the first time, we propose a semi-immersion strategy for the extraction of PAEs from water samples based on N-QTTI-coated SPME fibers. Combined with gas chromatography-mass spectrometry (GC-MS), the developed method N-QTTI-SPME-GC-MS exhibits a wide linear range with a satisfactory linearity (R2 ≥ 0.995). The limits of detection (LOD, S/N = 3) and the limits of quantification (LOQs, S/N = 10) were 0.17-1.70 and 0.57-5.60 ng L-1, respectively. The repeatability of the new method was examined using relative standard deviations (RSDs) between intraday and interday data, which were 0.38-7.98% and 1.22-6.60%, respectively. The spiked recoveries at three levels of 10, 100, and 1000 ng L-1 were in the range of 90.0-106.2% with RSDs of less than 7.48%. The enrichment factors ranged from 291 to 17180. When compared to previously published works, the LODs of the newly established method were improved 5-5400 times, and the enrichment factors were increased by at least 8 times. The absorption mechanism was investigated by X-ray photoelectron spectroscopy and noncovalent interaction force analysis. The technique was successfully employed for detecting PAEs in water samples.

Recent advances in analysis of capsaicin and its effects on metabolic pathways by mass spectrometry.

Capsaicin is the main food active component in Capsicum that has gained considerable attention due to its broad biological activities, including antioxidation, anti-inflammation, anti-tumor, weight regulation, cardiac protection, anti-calculi, and diurnal-circadian regulation. The potent biological effects of capsaicin are intimately related to metabolic pathways such as lipid metabolism, energy metabolism, and antioxidant stress. Mass spectrometry (MS) has emerged as an effective tool for deciphering the mechanisms underlying capsaicin metabolism and its biological impacts. However, it remains challenging to accurately identify and quantify capsaicin and its self-metabolites in complex food and biological samples, and to integrate multi-omics data generated from MS. In this work, we summarized recent advances in the detection of capsaicin and its self-metabolites using MS and discussed the relevant MS-based studies of metabolic pathways. Furthermore, we discussed current issues and future directions in this field. In-depth studies of capsaicin metabolism and its physiological functions based on MS is anticipated to yield new insights and methods for preventing and treating a wide range of diseases.

The impact of preoperative MRI-detected lateral meniscal intra-substance signal abnormalities on mid-term functional outcomes following mobile-bearing unicompartmental knee arthroplasty.

PURPOSE: There is a dilemma as to whether the presence of degenerative changes of lateral meniscus is a contraindication to medial unicompartmental knee arthroplasty (UKA). Therefore, the purpose of this study is to assess the influence of preoperative MRI-detected lateral meniscal intra-substance signal abnormalities on mid-term functional outcomes following mobile-bearing UKA. METHODS: We performed a retrospective review of the record on a consecutive series of patients who have undergone mobile-bearing medial UKA from September 2020 to June 2023. The mean duration of follow-up was 2.34 years. All records were collected from case system. MRI assessment of lateral meniscus was performed with the use of the Stoller's classification system. Patients were categorized into two groups (grade 0 and ≥ grade 1). Patient-reported outcomes were assessed with the use of the American Knee Society functional Score (AKSS-F), American Knee Society Objective Score (AKSS-O), and Oxford Knee Score (OKS) preoperatively and at latest follow-up. Furthermore, range of motion (ROM) and hip-knee-ankle angle (HKA) were measured in preoperative and postoperative periods. RESULTS: A total of 92 patients (101 knees) were included in our study. No differences in AKSS-F, AKSS-O, OKS, HKA, or ROM were found between those who showed normal or abnormal signal change of lateral meniscus preoperatively (P < 0.05). Furthermore, there were also no significant differences between two groups concerning AKSS-F, AKSS-O, OKS, HKA, or ROM at latest postoperative follow-up (P < 0.05). Age and duration of disease were independent predictors of low postoperative AKSS-F and AKSS-O (P < 0.05). Nevertheless, ROM was an independent predictor of high postoperative AKKS-O (P < 0.05). Age and female were independent predictors of high postoperative OKS (P < 0.05). CONCLUSION: The presence of preoperative MRI-detected lateral meniscal degenerative changes did not affect mid-term functional outcomes in patients who underwent mobile-bearing medial UKA. On the basis of the results of the current study, we believe that the presence of degenerative changes of lateral meniscus is acceptable in mobile-bearing medial UKA.

Minimally invasive small incision surgical technique for unicompartmental knee arthroplasty.

PURPOSE: It is always a challenge for orthopaedic surgeons to minimise surgical incisions while ensuring excellent surgical results. We propose the minimally invasive small incision (MISI) technique and an extramedullary positioning technique in the unicompartmental knee arthroplasty (UKA) surgery. This study aimed to clarify the early postoperative clinical outcomes and component alignment between MISI and conventional minimally invasive surgical (MIS) techniques. METHODS: We prospectively enrolled 60 patients who underwent MISI-UKA and 60 patients who underwent MIS-UKA as controls. Clinical parameters include the time of straight leg raising, postoperative walking time with walker assistance, hospital stay, Numerical Rating Scale (NRS) pain score and Knee Society Score (KSS). The postoperative components and lower extremity alignment were compared between the two groups with radiographic image measurement. RESULTS: The MISI group obtained a smaller incision during knee extension (P < 0.001) but a longer tourniquet usage time than the MIS group. The MISI group lost less blood (P < 0.001). The MISI group achieved straight leg raising and walking with aid earlier after surgery, with a shorter hospital stay than the MIS group (P < 0.001). Range of motion (ROM), NRS and KSS scores revealed no significant difference between the two groups in six months postoperative follow-up (P > 0.05). Radiographic measurement results between the two groups revealed no statistical difference (P > 0.05) CONCLUSION: The MISI-UKA could achieve faster earlier recovery after surgery and shorter hospital stays without compromising the principles of proper prosthesis position and limb alignment compared with the conventional MIS-UKA.

Intraoperative sensor technology quantifies inter-prosthesis pressure for predicting lower limb alignment after Oxford unicompartmental knee arthroplasty.

Purpose: The aim of this study is to quantify inter-prosthetic pressures at different knee angles in Oxford unicompartmental knee arthroplasty (OUKA) and its correlation with postoperative lower limb alignment. Methods: This study included 101 patients (122 knees) who underwent OUKA from March 2022 to July 2022. The previously designed matrix flexible force sensor was used to measure the inter-prosthesis pressure of different knee joint angles during the UKA operation, and the force variation trend and gap balance difference were obtained. The correlation between inter-prosthesis pressure and postoperative lower limb alignment index including hip-knee-ankle angle (HKAA) and posterior tibial slope (PTS) was analyzed. The effect of PTS change (ΔPTS) on the inter-prosthesis pressure and the range of motion (ROM) of the knee joint was analyzed. Radiographic and short-term clinical outcomes of included patients were assessed. Results: The inter-prosthesis pressure of the different knee joint angles during the operation was not consistent. The mean inter-prosthesis pressure and gap balance difference were 73.68.28 ± 41.65N and 36.48 ± 20.58N. The inter-prosthesis pressure at 0° and 20° was positively correlated with postoperative HKAA (p < 0.001). ΔPTS was positively correlated with the pressure at the end of knee extension and negatively correlated with the pressure at the end of knee flexion (p < 0.001). The HKAA, ROM, degree of fixed knee flexion deformity, and knee society score of the included patients were significantly improved compared with those before the operation (p < 0.001). Conclusion: The inter-prosthesis pressure measured at the knee extension position can predict postoperative HKAA to some degree. Changes in PTS will affect the inter-prosthesis pressure at the end of flexion and end of knee extension, but this change is not related to the range of motion of the knee joint.

Lateral meniscus with tears or with histologic calcification does not increase the risk of lateral osteoarthritis after medial unicompartmental arthroplasty.

PURPOSE: Meniscal tears or histological meniscal calcifications (in the absence of radiological chondrocalcinosis) are frequent in osteoarthritis. Whether lateral meniscal lesions influence clinical outcomes after medial unicompartmental knee arthroplasty (UKA) is unknown. METHODS: We analyzed 130 patients (130 knees) with medial unicompartmental knee arthroplasties between 2005 and 2015. These 130 knees had full articular cartilage thickness in the lateral compartment and no radiological chondrocalcinosis on preoperative radiographs. The lateral meniscus was analyzed with preoperative MRI and a biopsy of the anterior horn at the time of surgery. Synovial fluid was collected and analyzed for calcium pyrophosphate dihydrate crystal deposition (CPPD crystals). Lateral meniscal tears were untreated when detected on MRI or during surgery, with the hypothesis that these tears on the opposite compartment would remain asymptomatic in medial UKA. At average 10-year follow-up, patients were evaluated with clinical and radiographic outcome, with a focus on the risk of joint space narrowing of the lateral femorotibial compartment. RESULTS: CPPD crystals were present in the synovial fluid of 70 knees. Lateral meniscal tears were seen on MRI in 34 (49%) normal meniscuses of the 60 knees without CPPD crystals and in six other knees without histological meniscal calcification despite CPPD crystals. Histological calcification was present on 61 lateral meniscuses with 53 meniscal tears. The results showed no significant differences in the clinical outcomes between knees with lateral meniscal tears or lateral meniscal histological chondrocalcinosis or both lesions and those without these conditions. Additionally, radiographic progression of osteoarthritis in the opposite femorotibial compartment of the knee was not more frequent in patients with these meniscal issues. The ten year cumulative survival rates, measured by the need for total knee arthroplasty, were 91% for knees without meniscal lesions and 92% for knees with these lesions. CONCLUSION: On this basis, treatment of meniscal tears of the lateral compartment and routine aspiration of the knee to assess for birefringent crystals in the planning of medial UKA do not appear necessary.

A flexible electrochemical glucose sensing platform based on an electrospun PVA mat covered with in situ grown silver nanoparticles and a mixed self-assembled monolayer of glucose oxidase and ferrocene.

An electrochemical glucose sensor based on flexible materials is significant for wearable devices used for real-time health monitoring and diagnosis. However, applying flexible electrodes involves complex fabrication processes and might reduce detection sensitivity. To overcome these obstacles, we herein report a novel strategy for preparing a highly flexible enzyme electrode based on an electrospun poly(vinyl alcohol) (PVA) mat decorated with in situ grown silver nanoparticles (nano-Ag) for electrochemical glucose sensing. Ferrocene (Fc) was selected as an electron acceptor for glucose oxidase (GOD) in order to minimize the influence of oxygen. Electron transfer between GOD and Fc was facilitated by confining them within a mixed self-assembled monolayer (SAM) formed on a thin layer of gold deposited on top of the PVA/nano-Ag film. Nano-Ag was found to significantly increase the surface area of the electrode and improve the stability of electrode conductivity during tensile deformation. Electrochemical glucose detection was performed by chronoamperometry in the electroactivity domain of ferrocene, and good linearity (R2 = 0.993) was obtained in the range of 0.2-7 mM with a detection limit of 0.038 mM and a relative standard deviation (RSD) of 1.45% (n = 6). After being stuck to a bendable PDMS slice and bent, respectively, at 30° and 60° 50 times, the electrode showed slight changes in detection results (<4.78%), which remained within 8% when the bending angle increased to 90°. With its high flexibility, good detection performance, and convenient fabrication process, the proposed enzyme electrode showed good potential as a flexible platform for wearable glucose sensing systems.

Thermal/Redox-triggered release of pyrazinic functional molecules by coordination polymers with luminescence monitoring ability.

Storage of volatile active molecules, along with the prolongation of their specific functions, requires the use of regulatable carriers. Pyrazine derivatives are highly volatile compounds with a broad application owing to their flavoring, pharmaceutical, antimicrobial, antiseptic, and insecticidal properties. In this study, pyrazines were stored by coordinating them with cuprous iodide to easily generate a series of luminescent coordination polymer (CP)-based carriers. The CPs could respond to thermal-redox stimuli and manipulate pyrazine release by breaking the labile Cu-N bonds when triggered by the two stimuli. Moreover, the release process could be visualized by decreased luminescence caused by the gradual decomposition of CP structures. The loading efficiencies ranged from 31% to 38%, and the controlled release behaviors accord with the zero-order kinetics. This work is the first to prove that CPs could function as dual stimuli-mediated delivery systems, which hold the potential to control the release and strengthen the usability of functional molecules.

Multifunctionalized Covalent Organic Frameworks for Broad-Spectrum Extraction and Ultrasensitive Analysis of Per- and Polyfluoroalkyl Substances.

The contamination of surface and ground water by per- and polyfluoroalkyl substances (PFASs) has become a growing concern, and the structural diversity of PFASs is the major challenge for their ubiquitous applications. Strategies for monitoring coexistent anionic, cationic, and zwitterionic PFASs even at trace levels in aquatic environments are urgently demanded for effective pollution control. Herein, novel amide group and perfluoroalkyl chain-functionalized covalent organic frameworks (COFs) named COF-NH-CO-F9 are successfully synthesized and used for highly efficient extraction of broad-spectrum PFASs, attributing to their unique structure and the multifunctional groups. Under the optimal conditions, a simple and high-sensitivity method is established to quantify 14 PFASs including anionic, cationic, and zwitterionic species by coupling solid-phase microextraction (SPME) with ultrahigh-performance liquid chromatography-triple quadrupole mass spectrometry (UHPLC-MS/MS) for the first time. The established method displays high enrichment factors (EFs) of 66-160, ultrahigh sensitivity with low limits of detection (LODs) of 0.0035-0.18 ng L-1, a wide linearity of 0.1-2000 ng L-1 with correlation coefficient (R2) ≥0.9925, and satisfactory precision with relative standard deviations (RSDs) ≤11.2%. The excellent performance is validated in real water samples with recoveries of 77.1-108% and RSDs ≤11.4%. This work highlights the potential of rational design of COFs with the desired structure and functionality for the broad-spectrum enrichment and ultrasensitive determination of PFASs in real applications.

Predicting valgus malalignment after mobile-bearing UKA using a new method: the arithmetic HKA of the arthritic knee.

BACKGROUND: Valgus malalignment is one of the most common reasons for the progression of osteoarthritis in the lateral compartment of the knee after mobile-bearing unicompartmental knee arthroplasty (UKA). The arithmetic hip-knee-ankle angle (aHKA) of the Coronal Plane Alignment of the Knee (CPAK) classification could reflect the constitutional alignment of the arthritic knee. The purpose of this study was to observe the relationship between the aHKA and valgus malalignment after mobile-bearing UKA. METHODS: This retrospective study was conducted using 200 knees undergoing UKA from January 1, 2019, to August 1, 2022. These radiographic signs, including preoperative hip-knee-ankle angle (HKA), mechanical proximal tibial angle (MPTA), mechanical lateral distal femoral angle (LDFA), and postoperative HKA, were measured using standardized weight-bearing long-leg radiographs. Patients with postoperative HKA > 180° and postoperative HKA ≤ 180° were classified as the valgus group and non-valgus group, respectively. The aHKA was calculated as 180° + MPTA - LDFA in this study, which had the same meaning as that (aHKA = MPTA - LDFA) in the CPAK classification. The Spearman correlation analysis, the Mann-Whitney U test, the chi-square test, the Fisher's exact test, and multiple logistic regression were used in the study. RESULTS: Of the 200 knees included in our study, 28 knees were classified as the valgus group, while 172 knees were in the non-valgus group. The mean ± standard deviation (SD) of aHKA (all groups) was 177.04 ± 2.58°. In the valgus group, 11 knees (39.3%) had a value of aHKA > 180°, while 17 knees (60.7%) had a value of aHKA ≤ 180°. In the non-valgus group, 12 knees (7.0%) had a value of aHKA > 180°, while 160 knees (93.0%) had a value of aHKA ≤ 180°. In Spearman correlation analysis, aHKA was positively correlated with postoperative HKA (r = 0.693, p < 0.001). In univariate analysis, preoperative HKA (p < 0.001), LDFA (p = 0.02), MPTA (p < 0.001), and aHKA (p < 0.001) showed significant differences between the valgus and non-valgus groups. Variables with p < 0.1 in univariate analysis were further analyzed using multiple logistic regression analysis, and the variable-aHKA (> 180° vs ≤ 180°, odds ratio (OR) = 5.899, 95% confidence interval (CI) = 1.213 to 28.686, and p = 0.028) was expressed as the risk factor of postoperative valgus malalignment. CONCLUSION: The aHKA is correlated with the postoperative alignment of mobile-bearing UKA and a high aHKA (> 180°) will increase the risk of postoperative valgus malalignment. Therefore, mobile-bearing UKA should be performed with caution in patients with preoperative aHKA > 180°.