A kinetics-coupled multi-surface complexation model deciphering arsenic adsorption and mobility across soil types.

The diversity of soil adsorbents for arsenic (As) and the often-overlooked influence of manganese (Mn) on As(III) oxidation impose challenges in predicting As adsorption in soils. This study uses Mössbauer spectroscopy, X-ray diffraction of oriented clay, and batch experiments to develop a kinetic coupled multi-surface complexation model that characterizes As adsorbents in natural soils and quantifies their contributions to As adsorption. The model integrates dynamic adsorption behaviors and Mn-oxide interactions with unified thermodynamic and kinetic parameters. The results indicate that As adsorption is governed by five primary adsorbents: poorly crystalline Fe oxides, well crystalline Fe oxides, Fe-rich clay, Fe-depletion clay, and organic carbon (OC). Fe oxides dominate As adsorption at low As concentrations. However, at higher As concentrations, soils from carbonate strata, with higher content of Fe-rich clay, exhibit stronger As adsorption capabilities than soils from Quaternary sediment strata. The enrichment in Fe-rich clay can enhance the resistance of adsorbed As to reduction processes affecting Fe oxides. Additionally, extensive redox cycles in paddy fields increase OC levels, enhancing their As adsorption compared to upland fields. This model framework provides novel insights into the intricate dynamics of As within soils and a versatile tool for predicting As adsorption across diverse soils.

Risk stratification of stage II rectal mucinous adenocarcinoma to predict the benefit of adjuvant chemotherapy following neoadjuvant chemoradiation and surgery.

Background: The treatment strategy for stage II rectal mucinous adenocarcinoma (RMA) recommends neoadjuvant chemoradiotherapy (NCR) followed by total mesorectal excision (TME). However, the necessity of adjuvant chemotherapy (AC) remains controversial. Materials and methods: Chi-square test was used to assess the relationship between pathological classification, AC and clinicopathological characteristics. Kaplan-Meier (KM) curves and the log-rank test were utilized to analyze differences in overall survival (OS) and cancer-specific survival (CSS) among different groups. Cox regression identified prognostic factors. Nomogram was established utilizing the independent prognostic factors. X-tile divided patients into three risk subgroups. Results: Compared to RMA, rectal adenocarcinoma (RA) demonstrates longer OS and CSS in all and non-AC stage II patients, with no difference in OS and CSS for AC stage II patients. Propensity score matching analyses yielded similar results. Stratified analysis found that AC both improve OS of RA and RMA patients. Age, gender, pathologic T stage, regional nodes examined, and tumor size were identified as independent prognostic factors for RMA patients without AC. A nomogram was constructed to generate risk scores and categorize RMA patients into three subgroups based on these scores. KM curves revealed AC benefits for moderate and high-risk groups but not for the low-risk group. The external validation cohort yielded similar results. Conclusions: In summary, our study suggests that, compared to stage II RA patients, stage II RMA patients benefit more from AC after NCR. AC is recommended for moderate and high-risk stage II RMA patients after NCR, whereas low-risk patients do not require AC.

Safety and feasibility of robotic surgery for colon cancer patients with previous abdominal surgery: a propensity score-matching analysis.

Robotic surgery is widely used in gastrointestinal surgery. While the application of robotic surgery for colon cancer patients with previous abdominal surgery (PAS) remains controversial for the fear of intra-abdominal adhesions. This study was aimed to evaluate the safety and feasibility of robotic colectomy for patients with PAS. The medical records of colon cancer patients who underwent robotic surgery at our hospital from June 2015 to August 2020 were extracted and analyzed. Propensity score-matching (PSM) analysis was implemented to minimize selection bias. We compared perioperative outcomes and postoperative complications between the patients with PAS or with no PAS (NPAS). A total of 79 patients (PAS group) and 348 patients (NPAS group) were included in our study. After PSM, 79 patients of PAS group and 79 patients of NPAS group were selected for further analysis. We did not find statistical difference in operative time, estimated blood loss, lymph nodes retrieved, length of hospital stay and hospital costs between the two groups. No difference was noted in the incidence of postoperative complications, conversion to open surgery and mortality between the two groups. According to the results of multivariate analysis, PAS was not identified as risk factor for postoperative complications. Left hemicolectomy and perioperative transfusion were associated with postoperative complications. PAS did not negatively affect the outcomes of robotic colectomy. After individually preoperative assessment, robotic surgery could be performed feasibly and safely for colon cancer patients with PAS.

The benefits of adjuvant chemotherapy are associated with the kind of neoadjuvant therapy in stage ypI rectal cancer: evidence based on population analysis.

PURPOSE: The oncological role of adjuvant chemotherapy (ACT) remains debated in locally advanced rectal cancer (RC) after neoadjuvant therapy (NAT), especially ypI RC. In this study, we used population-based data to evaluate the benefits of ACT in stage ypI RC after NAT and surgery. Moreover, we tried to differentiate what kind of NAT (radiotherapy alone or chemoradiotherapy) was administered because this may affect the further efficacy of ACT. METHODS: All patients with stage ypI primary rectal malignancy were diagnosed in the SEER database between 2004 and 2017. The Kaplan-Meier method was applied to estimate the effects of ACT in survival analysis. Cox regression was performed to calculate the hazard ratio (HR) and the prognosis factors of survival. Propensity score matching (PSM) was used to balance the parameters between therapy groups. RESULTS: The overall cohort's median follow-up time was 105 months. For 5-year OS and CSS, there were no significant differences between the ACT ( +) and ACT (-) groups (p = 0.105; p = 0.788). However, subgroup analyses according to the kind of NAT found that ACT improved overall survival (OS) and cancer-specific survival (CSS) in patients who received neoadjuvant radiotherapy (nRT) (p < 0.001, p = 0.015). Among patients who received neoadjuvant chemoradiotherapy (nCRT), no significant survival benefits were found between the ACT ( +) and ACT (-) groups (p = 0.526, p = 0.288). CONCLUSION: Our population-based cohort study suggested that the efficacy of ACT was associated with the kind of NAT. The ACT provides survival benefits in stage ypI RC for patients who received nRT. However, among patients who received nCRT, ACT did not improve long-term survival.

Adjuvant chemotherapy improves long-term survival in pathologic stage III rectal mucinous adenocarcinoma after pre-operative chemoradiotherapy.

PURPOSE: The benefits of adjuvant chemotherapy remain debated rectal mucinous adenocarcinoma (MC). Our study aims to delve into the efficacy of adjuvant chemotherapy in pathologic stage III rectal MC by a large population-based database. METHODS: The Chi-square test was performed to examine the parameters between treatment groups. The overall survival (OS) and cancer-specific survival (CSS) of treatment groups were conducted by using the Kaplan-Meier method. The impact of factors on survival was assessed using Cox regression analyses. To balance the covariates and reduce the selection bias, we employed propensity score matching (PSM) to narrow the differences between treatment groups. RESULTS: The median follow-up time for overall patients was 80 months. In the pre-operative chemoradiotherapy (pre-CRT) group, patients who received adjuvant chemotherapy had significantly better 5-year OS and CSS. Multivariate analyses found that adjuvant chemotherapy was associated with better OS (p < 0.001, HR (95% CI): 0.66 (0.51-0.86)) and CSS (p = 0.012, HR (95% CI): 0.71 (0.54-0.93)). However, adjuvant chemotherapy was not an independent prognosis factor in both OS (p = 0.149, HR (95% CI): 0.76 (0.53-1.1); Supplement Table 1) and CSS (p = 0.183, HR (95% CI): 0.74 (0.48-1.15)) in patients who did not receive pre-CRT. After PSM, similar results were found in the pre-CRT and the no pre-CRT groups. CONCLUSION: In conclusion, our population-based retrospective cohort study indicates that the effects of adjuvant chemotherapy were associated with the pre-CRT status in patients with stage III rectal MC. In patients who underwent pre-CRT, the receipt of adjuvant chemotherapy was associated with better survival outcomes. Conversely, adjuvant chemotherapy does not seem to confer significant survival benefits to patients without pre-CRT.

Enantioselective ecotoxicity of the herbicide dichlorprop and complexes formed with chitosan in two fresh water green algae.

To reduce the leaching potential, to prevent groundwater contamination and to maintain the efficacy of a pesticide, natural polysaccharides have received increasing attention due to their biocompatibility and useful biological reactivity for controlled release formulations (CRFs) of pesticides. In this paper, the toxicities of the chiral herbicide dichlorprop (DCPP) and its complexes with chitosan molecules (DCPP-CS) and chitosan nanoparticles (DCPP-NP) to two different green algae were determined and compared. The inhibition rates of DCPP, DCPP-CS and DCPP-NP were determined at 24, 48, 72, 96, 120, 144, 168 h, and the results show that (S)-DCPP was more toxic to Chlorella vulgaris than (R)-DCPP, while the (R)-DCPP was more toxic to Scenedesmus obliquus than (S)-DCPP. The study also found that the chiral selectivity of DCPP to Chlorella vulgaris and Scenedesmus obliquus could be changed when DCPP was complexed with chitosan molecules (CS) or chitosan nanoparticles (NP). For Chlorella vulgaris, the order of inhibition was (R)-DCPP-CS > (S)-DCPP-CS and (R)-DCPP-NP > (S)-DCPP-NP; for Scenedesmus obliquus, the order was (S)-DCPP-CS > (R)-DCPP-CS and (S)-DCPP-NP > (R)-DCPP-NP. This phenomenon suggests that the enantioselective behaviors of chiral compounds might shift when interactions with other chiral receptors coexist in different biological environments. Additionally, chitosan molecules and chitosan nanoparticles also showed different toxicities, which could be ascribed to the difference in the physicochemical properties between CS and NP or the differences in the cell walls of the two fresh water green algae.

Effect of chitosan on the enantioselective bioavailability of the herbicide dichlorprop to Chlorella pyrenoidosa.

Chitosan, a natural polysaccharide, is widely regarded as a biocompatible and potential carrier for controlled-release drug formulations. However, the potential effect of chitosan on the environmental behavior of contaminants is poorly understood, especially on chiral chemicals. In this study, the changes in bioavailability of the chiral herbicide dichlorprop to Chlorella pyrenoidosa by chitosan were investigated. The dissipation of (S)-enantiomer in Chlorella pyrenoidosa culture media without chitosan was faster than that of the herbicidally active (R)-enantiomer, whereas it was inversed to (R)-enantiomer being faster than (S)-enantiomer when chitosan was added into the media. In the absence of chitosan, the toxicity of (R)-enantiomer to Chlorella pyrenoidosa was more potent than that of the (S)-enantiomer. On the contrary, in the presence of chitosan, (R)-enantiomer was less toxic than (S)-enantiomer. These observations clearly suggest that chitosan changed the enantioselective bioavailability of dichlorprop. Fluorescence spectroscopic analysis showed that the interaction between chitosan and dichlorprop enantiomers depended greatly on the steric structure of dichlorprop, which offers a possible explanation as to why the addition of chitosan changed the enantioselective dissipation of dichlorprop by Chlorella pyrenoidosa. This work suggests that the enantioselective behaviors of chiral compounds in the environment might be shifted when interactions with other chiral receptors coexist.

Spectroscopic investigations of the chiral interactions between lipase and the herbicide dichlorprop.

The enantioselective interaction between penicillium expansum alkaline lipase and chiral phenoxypropionic acid herbicide dichlorprop was studied by using UV differential spectrophotometry and fluorescence spectrophotometry in the presence of a pH 8, phosphate buffer solution. Chiral differences in the UV absorption and fluorescence spectra of lipase with dichlorprop were detected. (R)-Dichlorprop interacted the strongest with lipase as measured by both UV absorption and fluorescence spectrophotometry, followed by (Rac)-dichlorprop, while (S)-dichlorprop had the weakest interaction. The hydrophobic interaction seem to play the dominant role in the interactions and the (R)-enantiomer needed the minimum put of energy to drive the endothermic reaction, while the Rac-type and S-type compounds needed more for the reaction to take place. In the meantime, the catalytic hydrolysis of FDA with lipase show that (R)-DCPP could inhibit lipase the most strongly relatively at the same condition, perhaps because (R)-DCPP had a stronger combining effect and high enantiomeric selectivity on lipase than (Rac)-DCPP and (S)-DCPP.

Enantioselectivity in toxicity and degradation of dichlorprop-methyl in algal cultures.

Enantioselectivity in the toxicity and degradation of the herbicide dichlorprop-methyl (2,4-DCPPM) in algal cultures was studied. Enantioselectivity was clearly observed in the toxicity of racemic 2,4-DCPPM and its two enantiomers. R-2,4-DCPPM showed low toxicity to Chlorella pyrenoidosa and Chlorella vulgaris, but higher toxicity to Scenedesmus obliquus. The observed toxicity was ranked: R-2,4-DCPPM>S-2,4-DCPPM>>Rac-2,4-DCPPM; the toxicity of R-2,4-DCPPM was about 8-fold higher than that of Rac-2,4-DCPPM. Additionally, 2,4-DCPPM was quickly degraded, in the initial 12 h, and different algae cultures had different enantioselectivity for the 2,4-DCPPM enantiomers. There was no significant enantioselectivity for 2,4-DCPPM in Chlorella vulgaris in the initial 7 h. However, racemic 2,4-DCPPM was degraded by Scenedesmus obliquus quickly, in the initial 4 h, much quicker, in fact, than the S- or R-enantiomers (racemate>R->S-), indicating that the herbicide 2,4-DCPPM was absorbed enantioselectively by Scenedesmus obliquus. The rapid formation of 2,4-DCPP suggested that 2,4-DCPPM adsorbed by algal cells was catalytically hydrolyzed to the free acid, a toxic metabolite. The production rates of 2,4-DCPP were as follows: Scenedesmus obliquus>Chlorella pyrenoidosa>Chlorella vulgaris, consistent with the degradability of 2,4-DCPPM. Scenedesmus obliquus had quick, but different, degradative and uptake abilities for R-, S-, and Rac-2,4-DCPPM. The R- and S- enantiomers were not hydrolyzed in the first 12 h, while both enantiomers were hydrolyzed slowly after that. These results indicate that some physical and chemical properties of compounds are of importance in determining their enantioselective toxicity and degradation. The ester and its metabolite likely played an important role in enantioselective toxicity to the three algae.