Meta-analysis of Palliative Care on End-stage Quality of Life in Cancer Patients.

Objective: This study aimed to investigate the impact of palliative care on the quality of life, depressive state, and physical and psychological symptoms of patients with end-stage cancer. Methods: A systematic literature search of PubMed, Embase, and Scopus databases was conducted for randomized controlled trials (RCTs) published from May 2000 to June 2023, focusing on the impact of palliative care on end-stage cancer patients. The search utilized terms such as "palliative care," "cancer/tumor/malignancy," "terminal/end-stage/advanced," to identify studies meeting our inclusion criteria. Selected RCTs were evaluated for quality, and relevant data were extracted for meta-analysis. Results: Meta-analysis of 16 RCTs revealed that palliative care significantly improved depressive states [OR=-0.88, 95%CI (-1.55, -0.20), P = .01] and alleviated physical and psychological symptoms [OR=-2.38, 95%CI (-3.95, -0.81), P = .003] in end-stage cancer patients compared to conventional oncology care. However, the improvement in overall quality of life was not statistically significant (P > .05). Conclusion: Palliative care significantly enhances the mental and physical well-being of end-stage cancer patients by reducing depressive states and symptom burden, although its impact on overall quality of life requires further exploration.

Association between plasma maresin 1 and the risk of atherosclerotic cardiovascular disease in Chinese adults: A community-based cohort study.

BACKGROUND AND AIMS: It has been reported that maresin 1 (MaR1) is able to protect against the development of atherogenesis in cellular and animal models. This study was performed to investigate whether plasma MaR1 is associated with the risk of atherosclerotic cardiovascular disease (ASCVD) at the population level. METHODS AND RESULTS: The study included 2822 non-ASCVD participants from a community-based cohort who were followed for about 8 years. Hazard ratios (HRs) and 95% confidence intervals (95% CIs) for ASCVD events according to baseline MaR1 quartiles were calculated using the Cox proportional hazards model. During follow-up, a total of 290 new ASCVD cases were identified. The restricted cubic spline analysis indicated a linear dose-response association between plasma MaR1 and incident ASCVD. In addition, the adjusted-HR (95% CI) for ASCVD events associated with one standard deviation increase in MaR1 was 0.79 (0.68-0.91). Moreover, the adjusted-HRs (95% CIs) for ASCVD events associated with the second, third and fourth quartiles versus the first quartile of plasma MaR1 were 1.00, 1.04 (0.76, 1.42), 0.88 (0.64, 1.22) and 0.58 (0.41, 0.84), respectively. Mediation analyses showed that the association between MaR1 and incident ASCVD was partially mediated by small dense low-density lipoprotein cholesterol, with a mediation proportion of 9.23%. Further, the net reclassification improvement and integrated discrimination improvement of ASCVD risk were significantly improved when MaR1 was added to basic model established by conventional risk factors (all p < 0.01). CONCLUSIONS: Elevated plasma MaR1 concentrations are associated with a lower risk of ASCVD development.

Structure and properties of the acellular porcine cornea irradiated with 60Co-γ and electron beam and its histocompatibility.

Acellular porcine cornea (APC) has been used in corneal transplantation and treatment of the corneal diseases. Sterilization is a key step before the application of graft, and irradiation is one of the most commonly used methods. In this paper, APC was prepared by the physical freeze-thawing combined with biological enzymes, and the effects of the electron beam (E-beam) and cobalt 60 (60Co-γ) at the dose of 15 kGy on the physicochemical properties, structure, immunogenicity, and biocompatibility of the APC were investigated. After decellularization, the residual DNA was 20.86 ± 1.02 ng/mg, and the α-Gal clearance rate was more than 99%. Irradiation, especially the 60Co-γ, reduced the cornea's transmittance, elastic modulus, enzymatic hydrolysis rate, swelling ratio, and cross-linking degree. Meanwhile, the diameter and spacing of the collagen fibers increased. In the rat subcutaneous implantation, many inflammatory cells appeared in the unirradiated APC, while the irradiated had good histocompatibility, but the degradation was faster. The lamellar keratoplasty in rabbits indicated that compared to the E-beam, the 60Co-γ damaged the chemical bond of collagen to a larger extent, reduced the content of GAGs, and prolonged the complete epithelization of the grafts. The corneal edema was more serious within 1 month after the surgery. After 2 months, the thickness of the APC with the two irradiation methods tended to be stable, but that in the 60Co-γ group became thinner. The pathological results showed that the collagen structure was looser and the pores were larger, indicating the 60Co-γ had a more extensive effect on the APC than the E-beam at 15 kGy.

The association of depressive symptoms and medication adherence in asthma patients: The mediation effect of medication beliefs.

BACKGROUND: The significant role of depression in influencing medication beliefs, which are pivotal cognitive factors that strongly influence medication adherence, has been established. Poor adherence to asthma-controlled medication poses an significant barrier to achieving optimal asthma management. OBJECTIVE: To explore the potential mediating effects of medication beliefs on the relationship between depressive symptoms and medication adherence in patients with asthma. METHODS: Demographic and clinical characteristics, depressive symptoms, medication adherence, and medication beliefs were collected using questionnaires. Structural equation modeling, was utilized to model medication beliefs as mediators in the relationship between depressive symptoms and medication adherence. Bootstrapping was performed to analyze the mediation- and contrast-specific indirect effects of the two medication beliefs. RESULTS: Among the patients who participated in the study, 29.6 % with depressive symptoms were more prone to poor adherence and exhibited skepticism toward asthma medications. Depression had a direct effect (direct effect = -0.275, 95%CI: -0.369 to -0.190) and an indirect effect on adherence mediated by medication beliefs (indirect effect = -0.168, 95%CI: -0.224 to -0.121). The specific mediation effect of concern belief was stronger than that of necessity belief (difference = -0.076, 95%CI: -0.132 to -0.029). CONCLUSION: Depressive symptoms have a direct impact on medication adherence as well as an indirect effect mediated by beliefs about medication, particularly concerns belief.

Practical application for legacy acid mine drainage (AMD) prevention and treatment technologies in karst-dominated regions: A case study.

Acid mine drainage (AMD) from abandoned mines in karst-dominated regions in southwestern China was causing contamination of groundwater and surface streams. To avert the unwise decisions of "pollution first before treatment" during pre-mining, mid-mining and post-mining activities, this paper proposes a contaminant migration prevention technical framework covering 4 comprehensive processes. The formation mechanism of spring pollution, engineering remediation processes and contamination treatment effects were described in Longdong Spring. In 2018, the Longdong Spring water had Fe 33.83 mg/L and Mn 3.60 mg/L, exceeding the Chinese surface water standard (0.3 mg/L and 0.1 mg/L in GB 3838-2002) by 112 and 36 times, respectively. In 2020, after grout blocking, in situ treatment and wetland remediation, the highest Fe was 4.5 mg/L in a short period, and the spring water pollution days in this year were 42 days compared with the previous 320 spring water pollution days in 2018. In 2021, two years of remediation with the implementation of terminal remediation wetlands, the Fe was less than 0.03 mg/L compared with the previous 33.83 mg/L, and the water quality reached water standard (less than 0.3 mg/L). At present, Longdong Spring has become one of the most beautiful natural local landscapes.

Boron-Assisted Cobalt-Catalyzed C-H Methylation Using CO2 and H2.

C-H methylation of heteroarenes (e.g., indoles, pyrroles, etc.) is frequently applied in the synthesis of drug/biorelated compounds. We herein report the use of CO2/H2 as a methylation reagent for selective C-H methylation of indoles and pyrroles in the presence of cobalt/B(C6F5)3 cocatalysts. The Lewis acidic additive B(C6F5)3 is essential to achieving good reactivity for a broad scope of substituted indoles and pyrroles (20 examples, up to 92% yields). The C-H methylation is accomplished via the CO2 reduction/C-C bond formation/reduction sequence. Water is the only byproduct. This system based on the use of non-noble metal catalysts features an environmentally benign alternative for C-H methylation.

Long-term groundwater geochemical evolution induced by coal mining activities-a case study of floor confined limestone aquifer in Yaoqiao Coal Mine, Jiangsu, China.

Groundwater chemical composition can be changed due to long-term coal mining activities, but it was unclear how it was induced in Taiyuan Formation limestone (TFL) regarding the lack of relevant quantitative studies. The aim of this research is to improve understanding of the chemical composition changes in groundwater of L4 limestone in the coal mining area based on the available hydrochemical and hydrodynamical reports and studies during the period 1978-2020. The systematical analysis of the groundwater composition and field allows to make the hydrogeological characterization with the relatively independent blocks by the factor groups "Planar division & Vertical zonation" and "High water pressure, Poor recharge & Little water inflow," which determines different hydrochemical types and high TDS concentration. The long-term groundwater drainage has caused the eastern and southern limestone aquifer to demonstrate a wide range of depression cones and depletion of groundwater resources, the majority areas were dewatered, and the karstification process changed significantly. An analysis of chemical compositions changes due to extensive permanent drainage of L4 limestone water revealed the decrease in the TDS concentration. The solubility of calcite, dolomite, and gypsum changed, which resulted in the decreasing tendency of Ca2+ + Mg2+ ions. Evaporation and concentration were found to be the main factors determining the L4 limestone water composition, whereas ion exchange was the primary factor for rock-water interaction. These findings are helpful for mine enterprises to take necessary measures for preventing and controlling the groundwater quality degradation from the extensive coalmine drainage.

Structure and properties of the acellular porcine cornea irradiated with electron beam and its in-situ implantation.

Different sterilization doses of the electron beam (E-beam) will change the properties of biomaterials and affect their clinical application. Acellular porcine cornea (APC) is a promising corneal substitute to alleviate the shortage of corneal resources. The residual DNA was significantly reduced to 18.50 ± 3.19 ng/mg, and the clearance rate of α-Gal was close to 100% after the treatment with freezing-thawing combined enzyme, indicating that the decellularization was effective. The effects of different E-beam doses at 0, 2, 8, 15, and 25 kGy on the APC were studied. With the increase in irradiation dose, the transmittance, tensile strength, and swelling ratio of APC gradually decreased, but the resistance to enzymatic degradation was stronger than that of non-irradiated APC, especially at 8 kGy. The structure of APC was denser after irradiation, but the dose of 25 kGy could cause partial collagen fiber fracture and increase the pore size. The cell viability of the APC irradiated by 15 and 25 kGy were greater than 80%. After the implantation in rabbit corneas, there was no obvious neovascularization and inflammation, but the dose of 25 kGy had a more destructive effect on the chemical bonds of collagen, which made the APC easier to be degraded. The thickness of APC in the 25 kGy group was thinner than that in the 15 kGy group 1 year after surgery, and the epithelium grew more slowly, so the E-beam dose of 15 kGy might be more suitable for the sterilization of APC.

Palladium-Catalyzed Thiocarbonylation of Aryl Iodides Using CO2.

The first example of catalytic thiocarbonylation of aryl iodides using CO2 has been achieved employing a combination of PdCl2 and carbazole-derived phosphine ligands. Under mild conditions, a broad scope of aryl iodides were converted to the desired thioester products in the presence of aryl or alkyl thiols (33 examples, up to 96% yields). The choice of metal, ligands, and reductant were crucial for high efficiency and chemoselectivity. Moreover, this strategy provided an effective method for the late-stage functionalization of biorelevant molecules.

Serum metabolomics analysis in patients with alcohol dependence.

Objective: Alcohol dependence (AD) is a chronic recurrent mental disease caused by long-term drinking. It is one of the most prevalent public health problems. However, AD diagnosis lacks objective biomarkers. This study was aimed to shed some light on potential biomarkers of AD patients by investigating the serum metabolomics profiles of AD patients and the controls. Methods: Liquid chromatography-mass spectrometry (LC-MS) was used to detect the serum metabolites of 29 AD patients (AD) and 28 controls. Six samples were set aside as the validation set (Control: n = 3; AD group: n = 3), and the remaining were used as the training set (Control: n = 26; AD group: n = 25). Principal component analysis (PCA) and partial least squares discriminant analysis (PCA-DA) were performed to analyze the training set samples. The metabolic pathways were analyzed using the MetPA database. The signal pathways with pathway impact >0.2, value of p <0.05, and FDR < 0.05 were selected. From the screened pathways, the metabolites whose levels changed by at least 3-fold were screened. The metabolites with no numerical overlap in their concentrations in the AD and the control groups were screened out and verified with the validation set. Results: The serum metabolomic profiles of the control and the AD groups were significantly different. We identified six significantly altered metabolic signal pathways, including protein digestion and absorption; alanine, aspartate, and glutamate metabolism; arginine biosynthesis; linoleic acid metabolism; butanoate metabolism; and GABAergic synapse. In these six signal pathways, the levels of 28 metabolites were found to be significantly altered. Of these, the alterations of 11 metabolites changed by at least 3-fold compared to the control group. Of these 11 metabolites, those with no numerical overlap in their concentrations between the AD and the control groups were GABA, 4-hydroxybutanoic acid, L-glutamic acid, citric acid and L-glutamine. Conclusion: The metabolite profile of the AD group was significantly different from that of the control group. GABA, 4-hydroxybutanoic acid, L-glutamic acid, citric acid, and L-glutamine could be used as potential diagnostic markers for AD.

Dissolved organic matter composition and fluorescence characteristics of the river affected by coal mine drainage.

Coal mine drainage (CMD) discharged into surface waters results in serious environmental pollution risk to rivers, lakes, and reservoirs. Coal mine drainage generally contains a variety of organic matter and heavy metals due to coal mining activities. Dissolved organic matter (DOM) plays an important role in the physicochemical and biological processes of many aquatic ecosystems. In this study, the investigations were carried out in the dry and wet seasons in 2021 to assess the characteristics of DOM compounds in coal mine drainage and the CMD-affected river. The results indicated that the pH of CMD-affected river pressed close to coal mine drainage. Besides, coal mine drainage lowered DO by 36% and increased total dissolved solids by 19% in the CMD-affected river. Coal mine drainage decreased absorption coefficient a(350) and absorption spectral slope S275-295 of DOM in the CMD-affected river; hence, DOM molecular size increased with decreasing S275-295. Three-dimensional fluorescence excitation-emission matrix spectroscopy and parallel factor analysis identified humic-like C1, tryptophan-like C2, and tyrosine-like C3 in the CMD-affected river and coal mine drainage. DOM in the CMD-affected river mainly originated from microbial and terrestrial sources, with strong endogenous characteristics. The ultra-high-resolution Fourier transform ion cyclotron resonance mass spectrometry analysis revealed that coal mine drainage had a higher relative abundance of CHO (44.79%), with a higher unsaturation degree of DOM. Coal mine drainage decreased the AImod,wa, DBEwa (double bond equivalents), Owa, Nwa, and Swa values and increased the relative abundance of the O3S1 species with DBE of 3 and carbons number range of 15-17 at the CMD inlet to the river channel. Moreover, coal mine drainage with the higher protein content increased the protein content of water at the CMD inlet to the river channel and the downstream river. DOM compositions and proprieties in coal mine drainage were investigated to further understand the influence of organic matter on heavy metals in future study.

Development, Validation and Application of a Bridging ELISA for Detection of Antibodies against GQ1001 in Cynomolgus Monkey Serum.

Immunogenicity is a major issue associated with the PK, efficacy, and safety evaluation of therapeutic protein products during pre-clinical and clinical studies. A multi-tiered approach consisting of screening, confirmatory, and titration assays has been widely adopted for anti-drug antibody testing. GQ1001, a recombinant humanized anti-human epidermal growth factor receptor 2 monoclonal antibody covalently linked to a cytotoxin of DM1, possesses a novel format of antibody-drug conjugates. In this study, we reported the development, validation, and application of an acid-dissociation bridging enzyme-linked immunosorbent assay for the detection of antibodies against GQ1001 in cynomolgus monkey serum. The sensitivity of the screening assay was 126.141 ng/mL in undiluted serum. The screening assay and confirmatory assay were neither affected by the naïve monkey serum nor by 2% and 5% (v/v) erythrocyte hemolysates. Moreover, the assay was not subject to interference by 2500 ng/mL of human IgG1 in the samples. Drug interference at low positive control (150 ng/mL) and high positive control (8000 ng/mL) of anti-GQ1001 antibodies was not observed when GQ1001 concentrations were below 3.125 µg/mL and 100 µg/mL, respectively. Furthermore, no hook effect was observed for the positive antibodies in the concentration range of 8 to 64 µg/mL. The validated assay was, thereafter, successfully applied to a single-dose toxicity study of GQ1001. Anti-drug antibody positive rates among dosing animals and testing samples were reported, and no significant impact was found on toxicokinetic outcomes.

Deep Groundwater Flow Patterns Induced by Mine Water Injection Activity.

Mine water injection into deep formations is one of the effective approaches for reducing the drainage from coal mines in the arid and semi-arid region of the Ordos basin, China. Many coal mines are attempting to execute the related projects. Under the influence of groundwater protection, the understanding of regional groundwater flow is becoming highly important to the mine water monitoring, whereas quite few academic research teams focus on the deep groundwater flow pattern by mine water injection. This paper reveals the spatial distribution of Liujiagou Formation that is in positive correlation with the terrain, and its local thickness is influenced by the dominant W-E and NE-SW directions of geological structures. Only a part of sandstone rocks consists of aquifers, the rest 61.9% of relatively dry rock provide the enhanced storage space and partial mudstone aquicludes decrease the possibility of the vertical leakage for mine water. The dynamic storage capacity is evaluated at 2.36 Mm3 per 1 km2 and over 25.10 billion m3 in this study area. Two hydrogeologic cross-sections of basin-scale identify the W-E and N-S regional groundwater flow directions, with the lower Yellow River catchment becoming the discharged region. The hierarchically and steadily nested flow systems containing coal mining claims are influenced by coal mining activity. The groundwater depression cone in a shallow coal measure aquifer is caused by mine water drainage whereas the groundwater mound in Liujiagou Formation is generated by mine water injection activity. The numerical simulation revealed that the groundwater head rebound is slightly decreased and will not recover to its initial baseline within 500 years due to its low porosity and permeability. This study elucidates the deep groundwater flow patterns induced by mine water injection and provides a practical methodology for the management and pollution monitoring of mine water injection activity.

Synthesis of Chiral ß,ß-Disubstituted Ketones via CuH-Catalyzed Coupling of Aryl Alkenes and 3-Aryl-2H-azirines.

A CuH-catalyzed coupling of aryl alkenes with 3-aryl-2H-azirines has been developed to synthesize optically active ß,ß-disubstituted ketones. We propose that this protocol occurs through a sequence in which a chiral alkylcopper complex regioselectively attacks the N-C2 bonds of azirines to generate chiral ß-aryl imines, which additionally afford ketones upon hydrolysis. This method provides a novel complementary approach for synthesizing chiral ß,ß-disubstituted ketones in good yields with high levels of enantioselectivity under mild conditions.

Coal Mining Activities Driving the Changes in Microbial Community and Hydrochemical Characteristics of Underground Mine Water.

Coal mining can cause groundwater pollution, and microorganism may reflect/affect its hydrochemical characteristics, yet little is known about the microorganism's distribution characteristics and its influence on the formation and evolution of mine water quality in underground coal mines. Here, we investigated the hydrochemical characteristics and microbial communities of six typical zones in a typical North China coalfield. The results showed that hydrochemical compositions and microbial communities of the water samples displayed apparent zone-specific patterns. The microbial community diversity of the six zones followed the order of surface waters > coal roadways > water sumps ≈ rock roadways ≈ goafs > groundwater aquifers. The microbial communities corresponded to the redox sensitive indices' levels. Coal roadways and goafs were the critical zones of groundwater pollution prevention and control. During tunneling in the panel, pyrite was oxidized by sulfur-oxidizing bacteria leading to SO42- increase. With the closure of the panel and formation of the goaf, SO42- increased rapidly for a short period. However, with the time since goaf closure, sulfate-reducing bacteria (e.g., c_Thermodesulfovibrionia, Desulfobacterium_catecholicum, etc.) proportion increased significantly, leading to SO42- concentration's decrease by 42% over 12 years, indicating the long-term closed goafs had a certain self-purification ability. These findings would benefit mine water pollution prevention and control by district.

The Outer Membrane Vesicles of Salmonella enterica Serovar Typhimurium Activate Chicken Immune Cells through Lipopolysaccharides and Membrane Proteins.

Salmonella is a common pathogen which can secrete outer membrane vesicles (OMVs). However, the effect of OMVs from Salmonella enterica Serovar Typhimurium (S. Typhimurium) of poultry origin on cells of the chicken innate immune system is not well known. In this study, S. Typhimurium OMVs were first isolated from three different poultry strains of Salmonella, Salmonella CVCC542, SALA, and SALB. In order to investigate the effect of OMVs on the maturation of monocytes into macrophages, both bone marrow-derived (BMD) monocytes and macrophage cell line HD11 cells were used. OMVs promoted the formation of monocyte dendrites in both types of cells, enabled BMD cells to become larger, and stimulated expression of LPS-induced TNF-αfactor (LITAF), IL-6, and inducible nitric oxide synthase (iNOS) genes in HD11 cells. These results demonstrated the capability of OMVs to promote the development of chicken monocytes into macrophages and the maturation of macrophages. In order to study the effect of OMVs on the phagocytosis of macrophages, chicken spleen-derived monocytes and HD11 cells were used. Phagocytosis of FITC-Salmonella and FITC-dextran by these two types of cells was enhanced after stimulation with OMVs. To determine which components in OMVs were responsible for the above observed results, OMVs were treated with proteinase K(PK) or polymyxin B (PMB). Both treatments reduced the phagocytosis of FITC-Salmonella by HD11 cells and chicken spleen mononuclear cells and reduced the secretion of IL-1ß, LITAF, and IL-6 cytokines. These results demonstrated that Salmonella OMVs activated chicken macrophages and spleen mononuclear cells and the activation was achieved mainly through lipopolysaccharides and membrane proteins.

Effects of ambient temperature on outpatient visits for dermatitis in Xinxiang, China: a time-series analysis.

Previous studies have reported regional variations in the relationship between ambient temperature and dermatitis, which therefore remain inconclusive. This study aimed to understand the short-term effects of ambient temperature in outpatients with dermatitis in Xinxiang. Routine data of dermatitis outpatient visits between January 1, 2015, and December 31, 2018 were acquired from the First Affiliated Hospital of Xinxiang Medical University. A distributed lag nonlinear model (DLNM) in combination with a generalized additive model (GAM) was applied to investigate the acute impact of ambient temperature on dermatitis outpatients. Two stratified analyses based on age and sex were conducted to explore their potential modification effects. A total of 18,064 dermatitis outpatient records were retrieved during the study period. The relationship between ambient temperature and dermatitis outpatients was found to be nonlinear; exposure-response curves were approximately "J" shaped. The risk of dermatitis outpatient increased with a corresponding elevation in temperature from 11.5 to 27.5°C. However, the significance was lost when the temperature exceeded the given range. Stratified analysis demonstrated higher sensitivity to temperature in females than in males, and the young groups (<15 years) might be sensitive to heat temperature. This study provides first-hand epidemiological evidence demonstrating a higher risk of dermatitis outpatient visits associated with moderately higher temperatures. The outcomes of this study create awareness among citizens to take the necessary precautions to prevent the adverse effects of moderate heat temperature during early summer and autumn seasons.

Masks for COVID-19.

Sustainable solutions on fabricating and using a face mask to block the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) spread during this coronavirus pandemic of 2019 (COVID-19) are required as society is directed by the World Health Organization (WHO) toward wearing it, resulting in an increasingly huge demand with over 4 000 000 000 masks used per day globally. Herein, various new mask technologies and advanced materials are reviewed to deal with critical shortages, cross-infection, and secondary transmission risk of masks. A number of countries have used cloth masks and 3D-printed masks as substitutes, whose filtration efficiencies can be improved by using nanofibers or mixing other polymers into them. Since 2020, researchers continue to improve the performance of masks by adding various functionalities, for example using metal nanoparticles and herbal extracts to inactivate pathogens, using graphene to make masks photothermal and superhydrophobic, and using triboelectric nanogenerator (TENG) to prolong mask lifetime. The recent advances in material technology have led to the development of antimicrobial coatings, which are introduced in this review. When incorporated into masks, these advanced materials and technologies can aid in the prevention of secondary transmission of the virus.

Transformation kinetics and mechanism of gibberellic acid with ferrihydrite: Building a novel adsorption-transformation multi-step kinetic model.

Gibberellic acid (GA3), a widely used phytohormone, is easily transformed into more toxic products. The soil and groundwater environment are an important sink for GA3, but its transformation catalyzed by soil minerals has not been studied. In this study, the transformation kinetics and mechanism of GA3 with ferrihydrite (Fh) were examined through kinetic batch experiments, microscopic-spectroscopic investigation and mathematical modeling. The results showed that rapid adsorption of GA3 on Fh occurred in the first 4 h, followed by a catalytic pseudo-first-order transformation of the parent compound and products generation (4 h-30 d). Fh predominantly enhanced the transformation of GA3 into Iso-GA3 which was further hydrolyzed into OH-GA3, in which adsorption was a prerequisite for transformation. The catalytic transformation likely resulted from the surface hydroxy of Fh, which not only stabilized the transformation intermediates by forming surface complexes with the carboxyl group of GA3 and its products, but also served as a powerful nucleophile to attack the γ-lactone of GA3 and Iso-GA3. Based on the catalytic isomerization and hydrolysis mechanism of GA3 with Fh, a novel adsorption-transformation multi-step kinetic conceptual model and mathematical model were developed. This model fitted the measured data well (R2 > 0.97) and the fitted parameters suggested that the transformation rate constants of the transformation of GA3 into Iso-GA3 and the transformation of Iso-GA3 into OH-GA3 were facilitated with Fh by ∼26 and ∼9 times, respectively. The multi-step kinetic model has great potential in simulating GA3 fate in soil and groundwater to assess its environmental health risk.

Ligand- and Substrate-Controlled Chemodivergent Pd-Catalyzed Annulations of Cyclic ß-Keto Esters with 3-Aryl-2H-azirines.

Chemodivergent Pd-catalyzed annulations of cyclic ß-keto esters with 3-aryl-2H-azirines have been developed to provide rapid access to eight-membered ring lactams, bicyclic 3,4-dihydro-2H-pyrrole derivatives, and (E)-methyl [2-(2-oxocyclohexylidene)-2-phenylethyl]carbamates with high efficiency. The chemoselectivity can be determined by tuning the mono- or bisphosphine ligands as well as the substrate structure of cyclic ß-keto esters.