A multiview deep learning-based prediction pipeline augmented with confident learning can improve performance in determining knee arthroplasty candidates.

PURPOSE: Preoperative prudent patient selection plays a crucial role in knee osteoarthritis management but faces challenges in appropriate referrals such as total knee arthroplasty (TKA), unicompartmental knee arthroplasty (UKA) and nonoperative intervention. Deep learning (DL) techniques can build prediction models for treatment decision-making. The aim is to develop and evaluate a knee arthroplasty prediction pipeline using three-view X-rays to determine the suitable candidates for TKA, UKA or are not arthroplasty candidates. METHODS: A study was conducted using three-view (anterior-posterior, lateral and patellar) X-rays and surgical data of patients undergoing TKA, UKA or nonarthroplasty interventions from sites A and B. Data from site A were used to derive and validate models. Data from site B were used as external test set. A DL pipeline combining YOLOv3 and ResNet-18 with confident learning (CL) was developed. Multiview Convolutional Neural Network, EfficientNet-b4, ResNet-101 and the proposed model without CL were also trained and tested. The models were evaluated using metrics such as area under the receiver operating characteristic curve (AUC), accuracy, precision, specificity, sensitivity and F1 score. RESULTS: The data set comprised a total of 1779 knees. Of which 1645 knees were from site A as a derivation set and an internal validation cohort. The external validation cohort consisted of 134 knees. The internal validation cohort demonstrated superior performance for the proposed model augmented with CL, achieving an AUC of 0.94 and an accuracy of 85.9%. External validation further confirmed the model's generalisation, with an AUC of 0.93 and an accuracy of 82.1%. Comparative analysis with other neural network models showed the proposed model's superiority. CONCLUSIONS: The proposed DL pipeline, integrating YOLOv3, ResNet-18 and CL, provides accurate predictions for knee arthroplasty candidates based on three-view X-rays. This prediction model could be useful in performing decision making for the type of arthroplasty procedure in an automated fashion. LEVEL OF EVIDENCE: Level III, diagnostic study.

Triglyceride-Glucose Index Predicts Major Adverse Cardiovascular and Cerebrovascular Events in Patients with Atrial Fibrillation.

This study aimed to explore the relationship between the trajectory of the triglyceride-glucose (TyG) index and the occurrence of major adverse cardiovascular and cerebrovascular events (MACCE) in patients with atrial fibrillation (AF).This prospective study included 1979 patients with AF, who were initially selected from the Kailuan study. Patients of AF were split into four groups according to the value of TyG index. The clinical endpoint was MACCE, including myocardial infarction and ischemic stroke. Cox proportional hazard models were employed to examine the hazard ratio (HR) and 95% confidence interval (CI) for MACCE in various trajectory groups.The mean age of all patients with AF was 67.65 ± 11.15 years, and 1752 (88.53%) were male. Over a median follow-up duration of 5.31 years, in total 227 MACCE were recorded. MACCE cumulative incidence in Quartile 4 (26.96%) was significantly higher than those in other quartiles (P = 0.023). Multivariate Cox proportional hazards regression analysis showed that a higher TyG index (Quartile 4) was significantly and positively linked to MACCE in patients with AF (P = 0.023, HR: 2.103; 95% CI: 1.107-3.994).The evaluated TyG index is significantly associated with an increased risk of MACCE in patients with AF.

Carboxymethyl chitosan-modified UiO-66 for the rapid detection of fenpropathrin in grains.

Fenpropathrin residues in grain are potentially harmful to humans. Therefore, a fluorimetric lateral flow immunoassay using a zirconium-based organic skeleton (UiO-66) as a signal marker was developed for detecting fenpropathrin. Herein, carboxymethyl chitosan (CMCS) was used to modify UiO-66 and improve its water solubility to facilitate stable binding with sodium fluorescein (NaFL). This resulted in formation of a new fluorescent probe that is more suitable for lateral flow immunoassay (LFIA). The materials were characterized via electron microscopy, Fourier-transform infrared spectroscopy, and powder X-ray diffraction. CMCS and NaFL were successfully bound to UiO-66. Under optimized conditions, the constructed NaFL/UiO-66@CMCS-LFIA exhibited a good linear relationship within the range of 0.98-62.5 µg/L, with a detection limit of 3.91 µg/L. This probe was fourfold more sensitive than traditional colloidal gold nanoparticle-based LFIA. Finally, NaFL/UiO-66@CMCS-LFIA was successfully applied to detect fenpropathrin in wheat and maize samples. The detection limit was 1.56 µg/kg and recoveries ranged from 96.58 % to 118.56 %. This study provides a sensitive, stable, and convenient method for the rapid detection of pesticide residues.

Construction of a cleavable linker chemistry-based HBEXO-Chip to isolate circulating exosomes for breast cancer diagnosis.

Breast cancer is presently the most common form of malignant tumour globally, and its precise diagnosis is vital for enhancing patient survival rates and their quality of life. Exosomes, which are small extracellular vesicles containing proteins and nucleic acid molecules, have emerged as ideal cancer markers for liquid biopsy-based diagnostics. Nevertheless, the current methods for isolating exosomes present challenges for clinical implementation. Although immunoaffinity-based microfluidics hold potential for exosome-based cancer diagnostics, existing microfluidic chips struggle to capture and release intact, high-purity, and highly specific exosomes effectively. To surmount these obstacles, we developed the HBEXO-Chip, an innovative immunoaffinity microfluidic device that employs cleavable linker chemistry technology. This chip enables rapid isolation and detection of breast cancer-derived exosomes in peripheral blood. The fishbone-like microfluidic chip design of the HBEXO-Chip heightens the binding likelihood between specific exosomes and antibodies, significantly augmenting capture efficiency. Furthermore, the gentle reaction conditions of the cleavable linker chemistry retain the exosomes' membrane structure's integrity during the release process, which is advantageous for downstream experimental analysis. Our study demonstrated the effectiveness of the HBEXO-Chip in distinguishing breast cancer patients, patients with benign breast tumours, and healthy controls. By quantitatively analysing Epcam+ exosomes in clinical plasma samples, this technology platform provides a quick, user-friendly, highly sensitive, and specific assay for detecting tumour exosomes in peripheral blood, making it a valuable liquid biopsy tool for clinicians to diagnose breast cancer.

Manipulation of Cationic Group Density in Covalent Organic Framework Membranes for Efficient Anion Transport.

Anion exchange membranes with high anion conductivity are highly desired for electrochemical applications. Increasing ion exchange capacity is a straightforward approach to enhancing anion conductivity but faces a challenge in dimensional stability. Herein, we report the design and preparation of three kinds of isoreticular covalent organic framework (COF) membranes bearing tunable quaternary ammonium group densities as anion conductors. Therein, the cationic groups are integrated into the backbones by flexible ether-bonded alkyl side chains. The highly quaternary ammonium-group-functionalized building units endow COF membranes with abundant cationic groups homogeneously distributed in the ordered channels. The flexible side chains alleviate electrostatic repulsion and steric hindrance caused by large cationic groups, ensuring a tight interlayer stacking and multiple interactions. As a result, our COF membranes achieve a high ion exchange capacity and exceptional dimensional stability simultaneously. Furthermore, the effect of the ionic group density on the ion conductivity in rigid COF channels is systematically explored. Experiments and simulations reveal that the ionic group concentration and side chain mobility jointly determine the ion transport behavior, resulting in the abnormal phenomenon that the anion conductivity is not positively correlated to the ionic group density. The optimal COF membrane achieves the ever-reported highest hydroxide ion conductivity over 300 mS cm-1 at 80 °C and 100% RH. This study offers insightful guidelines on the rational design and preparation of high-performance anion conductors.

Residue dissipation dynamics and dietary risk assessment of emamectin benzoate, chlorantraniliprole, chlorfenapyr, and lufenuron in cabbage.

Emamectin benzoate (EB), chlorantraniliprole (CTP), chlorfenapyr (CFP), and lufenuron (LFR) are widely used to control Spodoptera exigua on cabbage. This study is aimed at establishing a universal, sensitive, accurate, and efficient method for the determination of these pesticide residues in cabbage using QuEChERS pretreatment combined with ultra-performance liquid chromatography or gas chromatography-tandem mass spectrometry (UPLC‒MS/MS or GC‒MS/MS). The recoveries of these pesticides (containing metabolites) in cabbage detected by the optimized method ranged between 80.9% and 99.9%, with relative standard deviations (RSDs) of 0.164-12.5%. The limit of quantification (LOQ) of the four pesticides was determined to be 0.01 mg/kg. The standard curve, accuracy, precision, and LOQ of the analysis method all met the requirements of pesticide residue detection. The optimized method was used to detect the dissipation dynamics and terminal residues in 12 regions. The dissipation half-lives of CTP, CFP, and LFR were 3.35-7.01 d, 2.29-4.75 d, and 3.24-6.80 d, respectively. The terminal residues of all these pesticides were below the maximum residue limits (MRLs). The dietary risk assessment indicated that the dietary risk probabilities for EB, CTP, CFP, and LFR were all less than 1 and were within the acceptable range. This study provides a comprehensive assessment of the residues and dietary risks of EB, CTP, CFP, and LFR for the scientific use of pesticides.

The terpene synthase (TPS) gene family in kiwifruit shows high functional redundancy and a subset of TPS likely fulfil overlapping functions in fruit flavour, floral bouquet and defence.

Volatile terpenes are important compounds that influence fruit flavour and aroma of kiwifruit. Terpenes in plants also impact on the floral bouquet and defence against pests and pathogens in leaves and fruit. To better understand the overlapping roles that terpenes may fulfil in plants, a systematic gene, chemical and biochemical analysis of terpenes and terpene synthases (TPS) was undertaken in Red5 kiwifruit (Actinidia spp.). Analysis of the Red5 genome shows it contains only 22 TPS gene models, of which fifteen encode full-length TPS. Thirteen TPS can account for the major terpene volatiles produced in different tissues of Red5 kiwifruit and in response to different stimuli. The small Red5 TPS family displays surprisingly high functional redundancy with five TPS producing linalool/nerolidol. Treatment of leaves and fruit with methyl jasmonate enhanced expression of a subset of defence-related TPS genes and stimulated the release of terpenes. Six TPS genes were induced upon herbivory of leaves by the economically important insect pest Ctenopseustis obliquana (brown-headed leaf roller) and emission, but not accumulation, of (E)- and (Z)-nerolidol was strongly linked to herbivory. Our results provide a framework to understand the overlapping biological and ecological roles of terpenes in Actinidia and other horticultural crops.

3D covalent organic framework membrane with fast and selective ion transport.

3D ionic covalent organic framework (COF) membranes, which are envisioned to be able to break the trade-off between ion conductivity and ion selectivity, are waiting for exploitation. Herein, we report the fabrication of a 3D sulfonic acid-functionalized COF membrane (3D SCOF) for efficient and selective ion transport, using dual acid-mediated interfacial polymerization strategy. The 3D SCOF membranes possess highly interconnected ion transport channels, ultramicroporous pore sizes (0.97 nm), and abundant sulfonate groups (with a high ion exchange capacity of 4.1 mmol g-1), leading to high proton conductivity of 843 mS cm-1 at 90 °C. When utilized in osmotic energy conversion, a high power density of 21.2 W m-2, and a remarkable selectivity of 0.976 and thus an exceptional energy conversion efficiency of 45.3% are simultaneously achieved. This work provides an alternative approach to 3D ionic COF membranes and promotes the applications of 3D COFs in ion transport and separation.

Study on Efficient Degradation of Waste PU Foam.

In this paper, the high-efficiency degradation and alcoholysis recovery of waste polyurethane foam were realized using a combination of a high-efficiency alkali metal catalyst (CsOH) and two-component mixed alcoholysis agents (glycerol and butanediol) in different proportions, using recycled polyether polyol and one-step foaming to prepare regenerated thermosetting polyurethane hard foam. The foaming agent and catalyst were adjusted experimentally to prepare regenerated polyurethane foam, and a series of tests were conducted on the viscosity, GPC, hydroxyl value, infrared spectrum, foaming time, apparent density, compressive strength, and other properties of the degradation products of the regenerated thermosetting polyurethane rigid foam. The resulting data were analyzed, and the following conclusions were drawn: The optimal conditions of alcoholysis were obtained when the mass ratio of glycerol to butanediol was 3:2, the amount of cesium hydroxide was 0.08%, the reaction temperature was 170 °C, and the reaction time was 2.5 h. Regenerated polyurethane foam with an apparent density of 34.1 kg/m3 and a compressive strength of 0.301 MPa was prepared under these conditions. It had good thermal stability, complete sample pores, and a strong skeleton. At this time, these are the best reaction conditions for the alcoholysis of waste polyurethane foam, and the regenerated polyurethane foam meets various national standards.

Observation of Enantiomeric Switching of Individual Plasmonic Metamolecules.

Active plasmonic metamolecules under microscopic observation are promising for optical reporters in single molecule sensing applications. While self-assembled reconfigurable chiral plasmonic metamolecules can be conveniently engineered with sensing functionalities, their observation is usually based on ensemble measurements, where the chiroptical response of enantiomers tend to cancel each other in ensemble circular dichroism. Herein, we demonstrate microscopic observation of enantiomeric switching of individual active DNA origami-assembled plasmonic metamolecules. The metamolecules are immobilized on a glass substrate in a microfluidic chamber, in which the plasmonic metamolecule can maintain their activities upon certain local stimuli as in solution. In circular differential scattering, two enantiomeric states controlled by the strand-displacement reaction display opposite spectral signals to each other, representing successful enantiomeric switching of the chirality. Moreover, in a close-to-racemic mixture of chiral metamolecules controlled by pH-sensitive strands, the coexistence of enantiomeric individuals, which is concealed in ensemble measurements, is clearly identified.

Study and Characterization of Regenerated Hard Foam Prepared by Polyol Hydrolysis of Waste Polyurethane.

In this paper, four different kinds of diols were used for the alcoholysis of waste thermoplastic polyurethane elastomers. The recycled polyether polyols were used to prepare regenerated thermosetting polyurethane rigid foam through one-step foaming. We used four different kinds of alcoholysis agents, according to different proportions of the complex, and we combined them with an alkali metal catalyst (KOH) to trigger the catalytic cleavage of the carbamate bonds in the waste polyurethane elastomers. The effects of the different types and different chain lengths of the alcoholysis agents on the degradation of the waste polyurethane elastomers and the preparation of regenerated polyurethane rigid foam were studied. Based on the viscosity, GPC, FT-IR, foaming time and compression strength, water absorption, TG, apparent density, and thermal conductivity of the recycled polyurethane foam, eight groups of optimal components were selected and discussed. The results showed that the viscosity of the recovered biodegradable materials was between 485 and 1200 mPa·s. The hard foam of the regenerated polyurethane was prepared using biodegradable materials instead of commercially available polyether polyols, and its compressive strength was between 0.131 and 0.176 MPa. The water absorption rate ranged from 0.7265 to 1.9923%. The apparent density of the foam was between 0.0303 and 0.0403 kg/m3. The thermal conductivity ranged from 0.0151 to 0.0202 W/(m·K). A large number of experimental results showed that the degradation of the waste polyurethane elastomers by the alcoholysis agents was successful. The thermoplastic polyurethane elastomers can not only be reconstructed, but they can also be degraded by alcoholysis to produce regenerated polyurethane rigid foam.

Intrinsic RIG-I restrains STAT5 activation to modulate antitumor activity of CD8+ T cells.

Antitumor activity of CD8+ T cells is potentially restrained by a variety of negative regulatory pathways that are triggered in the tumor microenvironment, yet, the exact mechanisms remain incompletely defined. Here, we report that intrinsic RIG-I in CD8+ T cells represents such a factor, as evidenced by observations that the tumor-restricting effect of endogenous or adoptively transferred CD8+ T cells was enhanced by intrinsic Rig-I deficiency or inhibition, with the increased accumulation, survival, and cytotoxicity of tumor-infiltrating CD8+ T cells. Mechanistically, T cell activation-induced RIG-I upregulation restrained STAT5 activation via competitive sequestering of HSP90. In accordance with this, the frequency of RIG-I+ tumor-infiltrating CD8+ T cells in human colon cancer positively correlated with attenuated survival and effector signatures of CD8+ T cells as well as poor prognosis. Collectively, these results implicate RIG-I as a potentially druggable factor for improving CD8+ T cell-based tumor immunotherapy.

Spacer-Engineered Ionic Channels in Covalent Organic Framework Membranes toward Ultrafast Proton Transport.

Side-chain engineering of covalent organic frameworks as advanced ion conductors is a critical issue to be explored. Herein, ionic covalent organic framework membranes (iCOFMs) with spacer-engineered ionic channel are de novo designed and prepared. The ionic channels are decorated with side chains comprising spacers having different carbon chain lengths and the -SO3 H groups at the end. Attributed to the synergistic contribution from the spacers and the -SO3 H groups, the iCOFM with moderate-length spacer exhibit the highest through-plane proton conductivity of 889 mS cm-1 at 90 °C.

Analysis of Factors Influencing the Efficiency of Catalysts Used in Waste PU Degradation.

Polyurethane (PU) is an indispensable part of people's lives. With the development of polyurethane, the disposal of polyurethane waste has become a significant issue around the world. Conventional degradation catalysts have poor dispersion and low degradation efficiency when used in the process of solid degradation into liquid. Therefore, this paper innovatively adopts self-made core-shell nanoscale titanium catalysis, traditional alkali metal catalyst (KOH), and polyol to carry out the glycolysis of waste polyurethane (PU) pipeline foam. The homogenized nanoscale titanium catalyst coated with alcohol gel has an obvious core-shell structure. The alcohol gel not only protects the catalyst but also dissolves with the alcoholysis agent in the process of glycolysis and disperses more evenly into the alcoholysis agent to avoid the phenomenon of nanocatalyst agglomeration, so as to facilitate catalytic cracking without reducing catalyst activity. In this study, investigated and compared the production of renewable polyurethane foam via a one-step method based on use of a homogeneous core-shell nanostructured titanium catalyst vs. a traditional alkaline catalyst in terms of the properties of regenerated polyether polyols as well as of the foams produced from these polyols. The physicochemical properties of regenerated polyether polyols that were analyzed included viscosity, hydroxyl value, and average molecular weight. The regenerated polyurethane foams were characterized based on water absorption, TG, SEM, and thermal conductivity analyses. The results show that, when the addition of homogeneous titanium catalyst was T2 0.050 wt.%, the viscosity of regenerated polyether polyols was the lowest, at 5356.7 mPa·s, which was reduced by 9.97% compared with those obtained using the alkali metal catalyst (KOH). When the amount of titanium catalyst was T3 0.075 wt.%, the hard foam made of regenerated polyurethane prepared by the catalyst showed the best properties, with a compressive strength of 0.168 MPa, which is 4.76% higher than that of the foam prepared using KOH catalyst.

Short hydrogen-bond network confined on COF surfaces enables ultrahigh proton conductivity.

The idea of spatial confinement has gained widespread interest in myriad applications. Especially, the confined short hydrogen-bond (SHB) network could afford an attractive opportunity to enable proton transfer in a nearly barrierless manner, but its practical implementation has been challenging. Herein, we report a SHB network confined on the surface of ionic covalent organic framework (COF) membranes decorated by densely and uniformly distributed hydrophilic ligands. Combined experimental and theoretical evidences have pointed to the confinement of water molecules allocated to each ligand, achieving the local enrichment of hydronium ions and the concomitant formation of SHBs in water-hydronium domains. These overlapped water-hydronium domains create an interconnected SHB network, which yields an unprecedented ultrahigh proton conductivity of 1389 mS cm-1 at 90 °C, 100% relative humidity.

Assembling covalent organic framework membranes via phase switching for ultrafast molecular transport.

Fabrication of covalent organic framework (COF) membranes for molecular transport has excited highly pragmatic interest as a low energy and cost-effective route for molecular separations. However, currently, most COF membranes are assembled via a one-step procedure in liquid phase(s) by concurrent polymerization and crystallization, which are often accompanied by a loosely packed and less ordered structure. Herein, we propose a two-step procedure via a phase switching strategy, which decouples the polymerization process and the crystallization process to assemble compact and highly crystalline COF membranes. In the pre-assembly step, the mixed monomer solution is casted into a pristine membrane in the liquid phase, along with the completion of polymerization process. In the assembly step, the pristine membrane is transformed into a COF membrane in the vapour phase of solvent and catalyst, along with the completion of crystallization process. Owing to the compact and highly crystalline structure, the resultant COF membranes exhibit an unprecedented permeance (water ≈ 403 L m-2 bar-1 h-1 and acetonitrile ≈ 519 L m-2 bar-1 h-1). Our two-step procedure via phase switching strategy can open up a new avenue to the fabrication of advanced organic crystalline microporous membranes.

Charged Nanochannels in Covalent Organic Framework Membranes Enabling Efficient Ion Exclusion.

Controllable ion transport through nanochannels is crucial for biological and artificial membrane systems. Covalent organic frameworks (COFs) with regular and tunable nanochannels are emerging as an ideal material platform to develop synthetic membranes for ion transport. However, ion exclusion by COF membranes remains challenging because most COF materials have large-sized nanochannels leading to nonselective transport of small ions. Here we develop ionic COF membranes (iCOFMs) to control ion transport through charged framework nanochannels, the interior surfaces of which are covered with arrayed sulfonate groups to render superior charge density. The overlap of an electrical double layer in charged nanochannels blocks the entry of co-ions, narrows their passageways, and concomitantly restrains the permeation of counterions via the charge balance. These highly charged large-sized nanochannels within the iCOFM enable ion exclusion while maintaining intrinsically high water permeability. Our results reveal possibilities for controllable ion transport based on COF membranes for water purification, ionic separation, sensing, and energy conversion.

Assembling covalent organic framework membranes with superior ion exchange capacity.

Ionic covalent organic framework membranes (iCOFMs) hold great promise in ion conduction-relevant applications because the high content and monodispersed ionic groups could afford superior ion conduction. The key to push the upper limit of ion conductivity is to maximize the ion exchange capacity (IEC). Here, we explore iCOFMs with a superhigh ion exchange capacity of 4.6 mmol g-1, using a dual-activation interfacial polymerization strategy. Fukui function is employed as a descriptor of monomer reactivity. We use Brønsted acid to activate aldehyde monomers in organic phase and Brønsted base to activate ionic amine monomers in water phase. After the dual-activation, the reaction between aldehyde monomer and amine monomer at the water-organic interface is significantly accelerated, leading to iCOFMs with high crystallinity. The resultant iCOFMs display a prominent proton conductivity up to 0.66 S cm-1, holding great promise in ion transport and ionic separation applications.

TPS-b family genes involved in signature aroma terpenes emission in ripe kiwifruit.

Aroma is a critical factor influencing consumer acceptability of ripe fruit. When fruit are eaten, the aroma travels retronasally from the mouth into the olfactory receptors located in the nose after exhaling. In kiwifruit (Actinidia spp.), terpene volatiles such as α-terpinolene and 1,8-cineole have been shown to contribute to the characteristic aroma of ripe fruit. Notably, 1,8-cineole contributes a key floral/eucalyptus note to the aroma of ripe A. chinensis 'Hort16A' kiwifruit, based on sensory descriptive and discriminant analysis. Emission of α-terpinolene and 1,8-cineole in kiwifruit is induced by ethylene, and production peaks when fruit are at eating ripeness. Two monoterpene synthase TPS-b family genes have been isolated from the fruit of A. arguta and A. chinensis that produce α-terpinolene and 1,8-cineole, respectively. Here we discuss terpene volatiles with respect to fruit aroma and consumer sensory evaluation, analyze the gene structure and conserved motifs of TPS-b genes in published kiwifruit genomes and then construct a transcriptional regulatory network based on Actinidia TPS-b. These data provide further insights into the potential molecular mechanisms underlying signature monoterpene synthesis to improve flavor in kiwifruit.

Scalable Fabrication of Crystalline COF Membranes from Amorphous Polymeric Membranes.

Covalent organic framework (COF) membranes hold potential for widespread applicability, but scalable fabrication is challenging. Here, we demonstrate the disorder-to-order transformation from amorphous polymeric membrane to crystalline COF membrane via monomer exchange. Solution processing is used to prepare amorphous membrane and the replacing monomer is selected based on the chemical and thermodynamical stability of the final framework. Reversible imine bonds allow the extraneous monomers to replace the pristine monomers within amorphous membrane, driving the transformation from disordered network to ordered framework. Incorporation of intramolecular hydrogen bonds enables the crystalline COF to imprint the amorphous membrane morphology. The COF membranes harvest proton conductivity up to 0.53 S cm-1 at 80 °C. Our strategy bridges amorphous polymeric and crystalline COF membranes for large-scale fabrication of COF membranes and affords guidance on materials processing.