Evaluation of Iron Chlorin e6 disappearance and hydrolysis in soil and garlic using salting-out assisted liquid-liquid extraction coupled with high-performance liquid chromatography and ultraviolet-visible detection.

Iron Chlorin e6 (ICE6), a star plant growth regulator (PGR) with independent intellectual property rights in China, has demonstrated its efficacy through numerous field experiments. We innovatively employed salting-out assisted liquid-liquid extraction (SALLE) with HPLC-UV/Vis to detect ICE6 residues in water, soil, garlic seeds, and sprouts. Using methanol and a C18 column with acetonitrile: 0.1% phosphoric acid mobile phase (55:45, v:v), we achieved a low LOQ of 0.43 to 0.77 µg kg-1. Calibration curves showed strong linearity (R2 > 0.992) within 0.01 to 5.00 mg kg-1. Inter-day and intra-day recoveries (0.05 to 0.50 mg kg-1) demonstrated high sensitivity and accuracy (recoveries: 75.36% to 107.86%; RSD: 1.03% to 8.78%). Additionally, density functional theory (DFT) analysis aligned UV/Vis spectra and indicated ICE6's first-order degradation (2.03 to 4.94 days) under various environmental conditions, mainly driven by abiotic degradation. This study enhances understanding of ICE6's environmental behavior, aids in risk assessment, and guides responsible use in agroecosystems.

Adsorption-desorption behavior of florpyrauxifen-benzyl on three microplastics in aqueous environment as well as its mechanism and various influencing factors.

Microplastics (MPs) and pesticides are two categories contaminants with proposed negative impacts to aqueous ecosystems, and adsorption of pesticides on MPs may result in their long-range transport and compound combination effects. Florpyrauxifen-benzyl, a novel pyridine-2-carboxylate auxin herbicide has been widely used to control weeds in paddy field, but the insights of which are extremely limited. Therefore, adsorption and desorption behaviors of florpyrauxifen-benzyl on polyvinyl chloride (PVC), polyethylene (PE) and disposable face masks (DFMs) in five water environment were investigated. The impacts of various environmental factors on adsorption capacity were evaluated, as well as adsorption mechanisms. The results revealed significant variations in adsorption capacity of florpyrauxifen-benzyl on three MPs, with approximately order of DFMs > PE > PVC. The discrepancy can be attributed to differences in structural and physicochemical properties, as evidenced by various characterization analysis. The kinetics and isotherm of florpyrauxifen-benzyl on three MPs were suitable for different models, wherein physical force predominantly governed adsorption process. Thermodynamic analysis revealed that both high and low temperatures weakened PE and DFMs adsorption, whereas temperature exhibited negligible impact on PVC adsorption. The adsorption capacity was significantly influenced by most environmental factors, particularly pH, cations and coexisting herbicide. This study provides valuable insights into the fate of florpyrauxifen-benzyl in presence of MPs, suggesting that PVC, PE and DFMs can serve as carriers of florpyrauxifen-benzyl in aquatic environment.

Design Criteria for Architected Materials with Programmable Mechanical Properties Within Theoretical Limit Ranges.

Architected materials comprising periodic arrangements of cells have attracted considerable interest in various fields because of their unconventional properties and versatile functionality. Although some better properties may be exhibited when this homogeneous layout is broken, most such studies rely on a fixed material geometry, which limits the design space for material properties. Here, combining heterogeneous and homogeneous assembly of cells to generate tunable geometries, a hierarchically architected material (HAM) capable of significantly enhancing mechanical properties is proposed. Guided by the theoretical model and 745 752 simulation cases, generic design criteria are introduced, including dual screening for unique mechanical properties and careful assembly of specific spatial layouts, to identify the geometry of materials with extreme properties. Such criteria facilitate the potential for unprecedented properties such as Young's modulus at the theoretical limit and tunable positive and negative Poisson's ratios in an ultra-large range. Therefore, this study opens a new paradigm for materials with extreme mechanical properties.

[Expression and characterization of mesophilic GH1 ß-glucosidase CdBglA from acidophilic Cuniculiplasma divulgatum].

ß-glucosidase has important applications in food, pharmaceutics, biomass conversion and other fields, exploring ß-glucosidase with strong adaptability and excellent properties thus has received extensive interest. In this study, a novel glucosidase from the GH1 family derived from Cuniculiplasma divulgatum was cloned, expressed, and characterized, aiming to find a better ß-glucosidase. The amino acid sequences of GH1 family glucosidase derived from C. divulgatum were obtained from the NCBI database, and a recombinant plasmid pET-30a(+)-CdBglA was constructed. The recombinant protein was induced to express in Escherichia coli BL21(DE3). The enzymatic properties of the purified CdBglA were studied. The molecular weight of the recombinant CdBglA was 56.0 kDa. The optimum pH and temperature were 5.5 and 55 ℃, respectively. The enzyme showed good pH stability, 92.33% of the initial activity could be retained when treated under pH 5.5-11.0 for 1 h. When pNPG was used as a substrate, the kinetic parameters Km, Vmax and Kcat/Km were 0.81 mmol, 291.99 µmol/(mg·min), and 387.50 s-1 mmol-1, respectively. 90.33% of the initial enzyme activity could be retained when CdBglA was placed with various heavy metal ions at a final concentration of 5 mmol/L. The enzyme activity was increased by 28.67% under 15% ethanol solution, remained unchanged under 20% ethanol, and 43.68% of the enzyme activity could still be retained under 30% ethanol. The enzyme has an obvious activation effect at 0-1.5 mol/L NaCl and can tolerate 0.8 mol/L glucose. In conclusion, CdBglA is an acidic and mesophilic enzyme with broad pH stability and strong tolerance to most metal ions, organic solvents, NaCl and glucose. These characteristics may facilitate future theoretical research and industrial production.

Hydrolysis of propyrisulfuron in water: Kinetics, influence of 34 environmental factors, transformation products identification, mechanisms and toxicities.

Propyrisulfuron is a novel sulfonylurea herbicide used for controlling annual grass and broad-leaved weeds in fields, but its fates and behaviors in environment are still unknown, which are of utmost importance for environmental protection. To reduce its potential environmental risks in agricultural production, the hydrolysis kinetics, influence of 34 environmental factors including 12 microplastics (MPs), disposable face masks (DFMs) and its different parts, 6 fertilizers, 5 ions, 3 surfactants, a co-existed herbicide of florpyrauxifen-benzy, humic acid and biochar, and the effect of MPs and DFMs on its hydrolysis mechanisms were systematically investigated. The main hydrolysis products (HPs), possible mechanisms, toxicities and potential risks to aquatic organisms were studied. Propyrisulfuron hydrolysis was an acid catalytic pyrolysis, endothermic and spontaneous process driven by the reduction of activation enthalpy, and followed the first-order kinetics. All environmental factors can accelerate propyrisulfuron hydrolysis to varying degrees except humic acid, and different hydrolysis mechanisms occurred in the presence of MPs and DFMs. In addition, 10 possible HPs and 7 possible mechanisms were identified and proposed. ECOSAR prediction and ecotoxicity testing showed that acute toxicity of propyrisulfuron and its HPs for aquatic organisms were low, but may have high chronic toxicity and pose a potential threat to aquatic ecosystems. The investigations are significantly important for elucidating the environmental fates and behaviors of propyrisulfuron, assessing the risks in environmental protection, and further providing guidance for scientific application in agro-ecosystem.

Degradation of a New Herbicide Florpyrauxifen-Benzyl in Water: Kinetics, Various Influencing Factors and Its Reaction Mechanisms.

Florpyrauxifen-benzyl is a novel herbicide used to control weeds in paddy fields. To clarify and evaluate its hydrolytic behavior and safety in water environments, its hydrolytic characteristics were investigated under varying temperatures, pH values, initial mass concentrations and water types, as well as the effects of 40 environmental factors such as microplastics (MPs) and disposable face masks (DFMs). Meanwhile, hydrolytic products were identified by UPLC-QTOF-MS/MS, and its hydrolytic pathways were proposed. The effects of MPs and DFMs on hydrolytic products and pathways were also investigated. The results showed that hydrolysis of florpyrauxifen-benzyl was a spontaneous process driven by endothermic, base catalysis and activation entropy increase and conformed to the first-order kinetics. The temperature had an obvious effect on hydrolysis rate under alkaline condition, the hydrolysis reaction conformed to Arrhenius formula, and activation enthalpy, activation entropy, and Gibbs free energy were negatively correlated with temperature. Most of environmental factors promoted hydrolysis of florpyrauxifen-benzyl, especially the cetyltrimethyl ammonium bromide (CTAB). The hydrolysis mechanism was ester hydrolysis reaction with a main product of florpyrauxifen. The MPs and DFMs did not affect the hydrolytic mechanisms but the hydrolysis rate. The results are crucial for illustrating and assessing the environmental fate and risks of florpyrauxifen-benzyl.

Long-term outcomes after coronary artery bypass graft with or without surgical ventricular reconstruction in patients with severe left ventricular dysfunction.

Background: Patients with chronic myocardial infarction (MI) and severe left ventricular (LV) dysfunction have poor clinical outcomes. This study aimed to determine whether coronary artery bypass graft (CABG) with surgical ventricular reconstruction (SVR) leads to further improvement in long-term patient outcomes compared with isolated CABG (I-CABG). Methods: From April 2010 to June 2013, 140 consecutive patients with chronic MI and severe LV dysfunction who received contrast-enhanced cardiovascular magnetic resonance imaging (CE-CMR) within 1 month before surgery were enrolled in this study. The cardiovascular events (CVEs) and long-term survival of patients who underwent CABG and SVR were compared with those who met the criteria for SVR but received I-CABG. Results: A total of 140 patients were included in the final analysis, including 70 patients who underwent CABG and SVR and 70 patients who underwent I-CABG. No differences were observed in the baseline characteristics, LV function, and late gadolinium enhancement (LGE) between the two groups. CABG+SVR patients experienced a longer cardiopulmonary bypass (CPB) time (116.0±35.0 vs. 100.2±23.8 minutes, P=0.002) and ventilation time [median (interquartile range): 22.0 (17.0, 37.0) vs. 20.0 (15.0, 24.0) hours, P=0.019] than I-CABG patients. During a mean follow-up of 123.1±12.7 months (range, 102-140 months), the CABG+SVR group had fewer rehospitalizations for congestive heart failure (CHF) (4.3% vs. 19.1%, P=0.007), but no statistical difference in the mortality rate was observed (2.9% vs. 4.4%, P=0.987). The cumulative CVE-free survival rate was significantly higher in CABG+SVR patients (87.0% vs. 67.6%, P=0.007). Conclusions: Our findings indicated that patients with chronic MI and severe LV dysfunction experienced similar perioperative outcomes after CABG+SVR or I-CABG. However, the CABG+SVR group resulted in fewer rehospitalizations for CHF and a higher cumulative CVE-free survival rate.

Constructing a Porous Structure on the Carbon Fiber Surface for Simultaneously Strengthening and Toughening the Interface of Composites.

The demand for both strength and toughness is perpetual in fiber-reinforced composites. Unfortunately, both properties are often mutually exclusive. As the mechanical properties of the composites are highly dependent on their interfacial properties, engineering interfaces between the fiber and matrix would be vital to overcome the conflict between strength and toughness. Herein, inspired by the physical interfacial architecture of grassroots-reinforced soil composites, a porous carbon nanotube-Mg(OH)2/MgO hybrid structure was constructed on the fiber surface via water electrolysis reaction and electrophoretic deposition process. The effects of the porous structure on the fiber filaments' mechanical properties, as well as the thickness on the interfacial properties, were all investigated. The results showed that fully covered porous structures on the fiber surface slightly enhanced the reliability of a single fiber in terms of mechanical properties by bridging the surface defects on the fiber. The interfacial shear strength and toughness of the porous structure-coated fiber/resin composite reached up to 92.3 MPa and 121.2 J/m2, respectively. These values were 61.30 and 121.98% higher than those of pristine fiber/resin composites, respectively. The strengthening effect was ascribed to the synergistic effects that improved numerous interfacial bonding areas and mechanical interlocking morphologies. The toughening mechanism was related to crack deflection, microcrack generation, and fracture of the porous structure during interfacial failure. Additional numerical studies by finite element analysis further proved the enhancement mechanism. Overall, the proposed method looks promising for producing advanced carbon fiber-reinforced polymer composites with excellent strength and toughness.

Efficient degradation of imidacloprid in soil by thermally activated persulfate process: Performance, kinetics, and mechanisms.

Imidacloprid (IMI) as a first-generation commercial neonicotinoid has been frequently detected in the environment in recent years. In this study, the efficient degradation of IMI in soil by a thermally activated persulfate (PS) process was investigated. The degradation efficiencies of IMI were in the range of 82-97% with the PS dosage of 10 mM, when the initial concentrations of IMI were 5-50 mg/kg in the soil. Degradation of the IMI was fitted with a pseudo-first-order kinetic model under different reaction temperatures. Inhibition effects of the common inorganic anions on the IMI degradation in the system followed the order Cl- > HCO3- > H2PO4- > NO3-. Soil pH and soil organic matter were also main factors affecting the degradation of IMI. The degradation efficiencies (64-97%) of three other typical neonicotinoids (acetamiprid, clothianidin, and dinotefuran) indicated that the thermally activated persulfate process could be used for remediation of neonicotinoid-contaminated soil. Quenching experiments indicated that the major reactive species in IMI degradation were SO4•-, O2•-, and •OH. Six degradation intermediates of IMI were inferred in the soil, and degradation pathways of IMI included hydroxylation, denitrification, C-N bond break and further oxidation.

Degradation and Pathways of Carvone in Soil and Water.

Carvone is a monoterpene compound that has been widely used as a pesticide for more than 10 years. However, little is known regarding the fate of carvone, or its degradation products, in the environment. We used GC-MS (gas chromatography-mass spectrometry) to study the fate of carvone and its degradation and photolysis products under different soil and light conditions. We identified and quantified three degradation products of carvone in soil and water samples: dihydrocarvone, dihydrocarveol, and carvone camphor. In soil, dihydrocarveol was produced at very low levels (≤0.067 mg/kg), while dihydrocarvone was produced at much higher levels (≤2.07 mg/kg). In water exposed to differing light conditions, carvone was degraded to carvone camphor. The photolysis rate of carvone camphor under a mercury lamp was faster, but its persistence was lower than under a xenon lamp. The results of this study provide fundamental data to better understand the fate and degradation of carvone and its metabolites in the environment.

Adsorption-desorption and transport behavior of pydiflumetofen in eight different types of soil.

Pydiflumetofen, a fungicide of the class of succinate dehydrogenase inhibitors, can disrupt energy metabolism by inhibiting the synthesis of succinate dehydrogenase, thus effectively inhibiting pathogenic fungal growth and related yield losses.We studied the adsorption and desorption behaviors and interaction mechanisms of pydiflumetofen in eight different arable soils by the infrared spectroscopy and batch equilibrium method. Pydiflumetofen adsorption and desorption property of soils conformed with the Freundlich isotherm model and the values for the adsorption capacity KF-ads were in the range of 14.592-102.610. The adsorption constants (KF-ads) exhibited a significantly positive and linear correlation (p < 0.1) with soil organic matter and organic carbon content. Both high and low temperatures weakened the pydiflumetofen sorption capacity of the soil. In addition, the initial pH of the solution, its ionic strength, and the addition of exogenous biochar, humic acid, and different types of surfactants at different concentrations also affected the sorption property of the soil. Pydiflumetofen is weakly mobile and leachable in most soils, and, poses some threat to surface soil and water organisms, but does not contaminate groundwater.

Adsorption-Desorption and Migration Behaviors of Oxaziclomefone in Different Agricultural Soils in China.

Oxaziclomefone is an organic heterocyclic herbicide which has been widely used in rice fields. The aim of this paper is to investigate the adsorption-desorption and migration of oxaziclomefone in four Chinese agricultural soils. All the four soils show high adsorption capacity for oxaziclomefone, with similar adsorption rates at 84.48%-96.70%. Four adsorption kinetic models were used to fit the adsorption kinetic characteristics and the elovich model was the best, indicating that chemical processes were involved in adsorption. For the isothermal adsorption behavior of oxaziclomefone, the Freundlich model shows the best, indicating that the adsorption sites for oxaziclomefone in soil were heterogeneous. The retention factor in the soil thin-layer plates ranges from 0.083 to 0.250 and the retention factor 0-10 cm layer of the soil column was > 50, indicating that the herbicide was not easily migration from all four soils. Because oxaziclomefone has low mobility in different soils and is not easily leached, it poses a low potential threat of contaminating surface water and groundwater.

Effects of left atrial appendage surgical treatment on the incidence of ischemic cerebrovascular accidents in patients with atrial fibrillation undergoing cardiac surgery.

BACKGROUND: We sought to assess different surgical methods for left atrial appendage treatment to determine whether any could reduce the incidence of atrial fibrillation-related long-term ischemic cerebrovascular accidents. METHODS: A total of 1243 patients were treated with left atrial appendage removal, and 107 patients (8.6%) were lost to follow-up and excluded. The primary outcome was the long-term incidence of ischemic cerebrovascular events (ie, ischemic stroke, excluding transient ischemic attack) and all-cause mortality. RESULTS: Of the 1136 patients, 37 (3.3%) had ischemic cerebrovascular events. The 1-year, 5-year, and 10-year freedoms from long-term ischemic cerebrovascular events of the left atrial appendage extracardiac ligation group were 99.7%, 94.0%, and 90.8%, respectively. The 1-year, 5-year, and 10-year survivals of the left atrial appendage intracardiac suture group were 99.7%, 94.6%, and 93.6%, respectively. There was a significant difference between the left atrial appendage extracardiac ligation group and the left atrial appendage excision group (P = .041). Seventeen patients (4.6%) had long-term ischemic cerebrovascular events in the left atrial appendage extracardiac ligation group (1.1% per year), 14 patients (3.5%) in the left atrial appendage intracardiac suture group (0.9% per year), and 6 patients (1.7%) in the left atrial appendage excision group (0.44% per year). Left atrial appendage excision can reduce the occurrence of long-term thrombotic stroke compared with left atrial appendage extracardiac ligation (95% confidence interval, 1.09-9.26; P = .035). CONCLUSIONS: For patients with atrial fibrillation, the removal of the left atrial appendage can effectively prevent stroke caused by atrial fibrillation.

Determination of the residue behavior of isocycloseram in Brassica oleracea and soil using the QuEChERS method coupled with HPLC.

Isocycloseram is a new isoxazoline insecticide that can efficiently control the diamondback moth in cruciferous crops. The aim of this study was to establish a method for the determination of isocycloseram residues in/on cabbage and in the soil using HPLC-UV at 264 nm. A field test was conducted in December 2019 and 2020 to monitor isocycloseram dissipation in Jiangxi, China. Acetonitrile was used to extract isocycloseram from cabbage and soil. C18 and GCB were used to purify cabbage extracts, whereas soil extracts did not require purification. At the addition level of 0.01-1.0 mg/kg, the average recoveries in cabbage and soil were 91.81-109.95% and 89.89-104.08% respectively. After having applied 10% isocycloseram DC, isocycloseram dissipated faster in the cabbage matrix. Isocycloseram residues on cabbage leaves could be removed through simple cleaning methods, especially by soaking in 2% citric acid.

Risk Factors for Aortic Regurgitation Progression After Repair of Sinus of Valsalva Aneurysm.

BACKGROUND: The main treatment for a ruptured sinus of Valsalva aneurysm (SVA) is surgical repair. Postoperative progression of aortic regurgitation (AR) following SVA repair increases the risk of reoperation, which decreases the long-term survival. Thus, identifying the risk factors for postoperative AR progression is of great significance. METHODS: Adult patients who were diagnosed with ruptured SVA and underwent surgical repair at the current centre were reviewed. Necessary data in the institutional database were extracted. The perioperative and follow-up assessments of the aortic valve by transthoracic echocardiography were also obtained. The aortic regurgitation progression was grouped into three categories: newly developing, recurrence, and worsening. Sixteen (16) variables were screened to identify potential risk factors by univariate logistic regression analysis or Chi-squared test. Variables with p-values <0.1 were further analysed by multivariate logistic regression models to find independent risk factors. RESULTS: A total of 198 consecutive patients from June 2006 to January 2018 were included. The overall incidence of postoperative AR progression was 19.2% (38 of 198). After the univariate analysis, SVA originating from the right coronary sinus, coexisting with ventricular septal defect, larger diameter of aortic annulus, and larger cardiothoracic ratio were screened as potential risk factors. Multivariate analysis indicated that coexisting with a ventricular septal defect (VSD) (OR, 2.82; 95% CI, 1.217-6.532; p=0.016) and larger cardiothoracic ratio (OR, 1.061; 95% CI, 1.001-1.124; p=0.047) were independent risk factors for postoperative AR progression. CONCLUSIONS: To prevent postoperative AR progression after surgical repair, more careful inspection and appropriate surgical techniques are necessary for patients coexisting with VSD or with a larger cardiothoracic ratio.

Determination of Pydiflumetofen Residues in Rice and its Environment by an Optimized QuEChERS Method Coupled with HPLC-MS.

Pydiflumetofen is a new succinate dehydrogenase inhibitor fungicide, and the method for determination of its residues in rice and associated environmental samples has not yet been reported. Here, we optimized, Quick Easy, Cheap, Effective, Rugged, Safe (QuEChERS) method for sample preparation, and used high performance liquid chromatography-tandem mass spectrometry (HPLC-MS) to detect the residual amounts of pydiflumetofen in rice and its environment. The results showed that there was a good linearity over the pydiflumetofen concentration range of 0.01-0.1 mg/L in all matrices (R2 > 0.99). At the spiked levels of 0.01, 0.05, and 0.1 mg/kg, the recovery rates of pydiflumetofen from various matrices were between 84.23 and 105.10 %, with the relative standard deviation of 1.07-9.99 %. The limit of detection (signal-to-noise ratio = 3) of the proposed method for pydiflumetofen was in the range of 1.9-3.5 µg/kg, and the limit of quantification (signal-to-noise ratio = 10) was in the range of 6.3-11.7 µg/kg.

Dissipation of tiafenacil in five types of citrus orchard soils using the HPLC-MS coupled with the quick, easy, cheap, effective, rugged, and safe method.

Tiafenacil is a new contact herbicide and its environmental behavior after field application remains poorly understood. In order to understand the dissipation of tiafenacil in the soil, the tiafenacil dissipation experiment was conducted at citrus orchard sites in five provinces of China (Gansu, Shandong, Sichuan, Jiangxi, and Hainan) in 2019 and 2020 (July-August) and the relevant determination methods were optimized. The results showed that the established method showed good linearity in the concentration range of 0.01-0.5 mg/kg. The average recoveries of tiafenacil from the five soils were 86.31-101.66%, with coefficients of variation of 0.28-10.79%. The dissipation of tiafenacil at the five experimental sites conformed to the first-order kinetic equation, Ct  = C0 exp- kt (R2  = 0.8130 - 0.9967). The half-life of tiafenacil ranged from 0.26 to 4.19 days. The dissipation rate of tiafenacil was positively correlated with soil organic matter content and negatively correlated with soil pH, while monthly average temperature and total rainfall were less influential than soil properties. Therefore, the established method was simple and effective for tiafenacil residue analysis in citrus orchard soils. Tiafenacil could readily dissipate in soil and might be a safe alternative to glyphosate for weed control in citrus orchards.

Extracardiac Tricuspid Annuloplasty: A Novel Technique for Functional Tricuspid Regurgitation.

We report 3 cases of functional tricuspid regurgitation and demonstrate a novel tricuspid repair technique through the right atrioventricular groove without cardiopulmonary bypass or open heart surgery, which provides a new idea for the treatment of functional tricuspid regurgitation.

The sesquiterpenes from the stem and leaf of Clausena lansium with their potential antibacterial activities.

Two new C13-norsesquiterpenes claulanterpene A (1) and B (2), together with two known sesquiterpenes (3-4), were isolated from methanol extract of the stem and leaf of Clausena lansium collected from Qingyuan county, Guangdong Province, China. Their structures were elucidated on the base of extensive spectroscopic analysis and comparison with data reported in the literature. Among them, compound 4 showed antibacterial activity against Bacillus cereus.