Synthesis of N-arylsulfonamides through a Pd-catalyzed reduction coupling reaction of nitroarenes with sodium arylsulfinates.

A novel one-step direct reductive coupling reaction between nitroarenes and sodium arylsulfinates was realized in the presence of an inexpensive Pd/C catalyst. In this procedure, readily available nitroarenes are employed as the nitrogen sources, and sodium arylsulfinates serve as both coupling partners and reductants. The method features high efficiency by using cheap Pd/C with low catalyst loading and good functional group tolerance in the absence of any additional reductants or ligands. This facile and mild synthetic method enables the high efficiency synthesis of functionalized N-arylsulfonamides from readily available substrates.

Ultrasound-based deep learning radiomics nomogram for risk stratification of testicular masses: a two-center study.

OBJECTIVE: To develop an ultrasound-driven clinical deep learning radiomics (CDLR) model for stratifying the risk of testicular masses, aiming to guide individualized treatment and minimize unnecessary procedures. METHODS: We retrospectively analyzed 275 patients with confirmed testicular lesions (January 2018 to April 2023) from two hospitals, split into training (158 cases), validation (68 cases), and external test cohorts (49 cases). Radiomics and deep learning (DL) features were extracted from preoperative ultrasound images. Following feature selection, we utilized logistic regression (LR) to establish a deep learning radiomics (DLR) model and subsequently derived its signature. Clinical data underwent univariate and multivariate LR analyses, forming the "clinic signature." By integrating the DLR and clinic signatures using multivariable LR, we formulated the CDLR nomogram for testicular mass risk stratification. The model's efficacy was gauged using the area under the receiver operating characteristic curve (AUC), while its clinical utility was appraised with decision curve analysis(DCA). Additionally, we compared these models with two radiologists' assessments (5-8 years of practice). RESULTS: The CDLR nomogram showcased exceptional precision in distinguishing testicular tumors from non-tumorous lesions, registering AUCs of 0.909 (internal validation) and 0.835 (external validation). It also excelled in discerning malignant from benign testicular masses, posting AUCs of 0.851 (internal validation) and 0.834 (external validation). Notably, CDLR surpassed the clinical model, standalone DLR, and the evaluations of the two radiologists. CONCLUSION: The CDLR nomogram offers a reliable tool for differentiating risks associated with testicular masses. It augments radiological diagnoses, facilitates personalized treatment approaches, and curtails unwarranted medical procedures.

Size-dependent effect of microplastics on toxicity and fate of diclofenac in two algae.

Microplastics (MPs) are frequently detected in natural waters and usually acted as vectors for other pollutants, leading to possible threats to aquatic organisms. This study investigated the impact of polystyrene MPs (PS MPs) with different diameters on two algae Phaeodactylum tricornutum and Euglena sp., and the combined toxicity of PS MPs and diclofenac (DCF) in two algae was also studied. Significant inhibition of P. tricornutum was observed after 1 d exposure of 0.03 µm MPs at 1 mg L-1, whereas the decreased growth rate of Euglena sp. was recovered after 2 d exposure. However, their toxicity decreased in the presence of MPs with larger diameters. The oxidative stress contributed a major for the size-dependent toxicity of PS MPs in P. tricornutum, while in Euglena sp. the toxicity was mainly caused by a combination of oxidative damage and hetero-aggregation. Also, PS MPs alleviated the toxicity of DCF in P. tricornutum and the DCF toxicity continually decreased as their diameter increased, whereas the DCF at environmentally concentration could weaken the toxicity of MPs in Euglena sp. Moreover, the Euglena sp. revealed a higher removal for DCF, especially in the presence of MPs, but the higher accumulation and bioaccumulation factors (BCFs) indicated a possible ecological risk in natural waters. The present study explored discrepancy on the size-dependent toxicity and removal of MPs associated with DCF in two algae, providing valuable data for risk assessment and pollution control of MPs associated with DCF.

Individual and combined toxicity of silver nanoparticles and triclosan or galaxolide in the freshwater algae Euglena sp.

With the widespread production and usage, silver nanoparticles (AgNPs) can be extensively found in the aquatic environment and co-exist with other pollutants for a prolonged time, leading to a more complex ecological risk in natural waters. In this work, the model freshwater algae Euglena sp. was selected to study the toxicity of AgNPs and explore their influences on the toxicity of two frequently detected personal care products, triclosan (TCS) and galaxolide (HHCB). The LC-MS targeted metabolomics was used to analyze the possible toxicity mechanism at the molecular level. Results showed that AgNPs was toxic to Euglena sp. upon 24 h exposure, but the toxicity decreased gradually as exposure times increased. AgNPs (<100 µg L-1) attenuated TCS and HHCB toxicity to Euglena sp., which could be attributed primarily to the decreased oxidative stress. Metabolomic analysis revealed that AgNPs induced a stress on algal defense system upon TCS exposure, but promoted the algal defense system upon HHCB exposure. Furthermore, DNA or RNA biosynthesis was accelerated in algae exposed to TCS or HHCB after the addition of AgNPs, implying that AgNPs may mitigate the genetic toxicity of TCS or HHCB in Euglena sp. These results emphasize the potential of metabolomics to reveal toxicity mechanism and provide new perspectives on the aquatic risk assessment of personal care products in the presence of AgNPs.

The combined toxicity of silver nanoparticles and typical personal care products in diatom Navicula sp.

Toxicity of silver nanoparticles (AgNPs) at environmentally relevant concentrations has been received an increasing attention, and their influence on the bioavailability of personal care products has been seldom studied. Here, the toxicity of AgNPs in typical diatom Navicula sp. was explored, and their influence on the bioavailability of typical personal care products such as triclosan (TCS) and galaxolide (HHCB) was also investigated. The underlying toxicity mechanisms were explored using liquid chromatography-mass spectrometry (LC-MS)-based metabolomics. Low concentrations of AgNPs (10 and 50 µg L-1) induced no observable responses of Navicula sp., in terms of growth rate, chlorophyll contents, and malondialdehyde accumulation. Furthermore, low doses of AgNPs could attenuate TCS or HHCB toxicity to Navicula sp., which was mainly attributed to the reduced oxidative stress. Metabolomics revealed that the disruption of DNA or RNA synthesis and instability of cytokinin-like substances may be also the reasons for the toxicity of AgNPs and TCS to Navicula sp. The damaged algal photosynthesis exposed to HHCB may be recovered by AgNPs, and the presence of signal chemicals (dehydrophytosphingosine and cardamonin) also showed a recovered algal growth. These results emphasize the potential of metabolomics to reveal toxicity mechanism, providing a new perspective on the aquatic risk assessment of nanoparticles and emerging organic pollutants.

Organic binding iron formation and its mitigation in cation exchange resin assisted anaerobic digestion of chemically enhanced primary sedimentation sludge.

Fe based chemically enhanced primary sedimentation (CEPS) is an effective method of capturing the colloidal particles and inorganic phosphorous (P) from wastewater but also produces Fe-CEPS sludge. Anaerobic digestion is recommended to treat the sludge for energy and phosphorus recovery. However, the aggregated sludge flocs caused by the coagulation limited sludge hydrolysis and P release during anaerobic digestion process. In this study, cation exchange resin (CER) was employed during anaerobic digestion of Fe-CEPS sludge with aims of prompting P release and carbon recovery. CER addition effectively dispersed the sludge flocs. However, the greater dispersion of sludge flocs could not translate to higher sludge hydrolysis. The maximum hydrolysis and acidification achieved at lower CER dosage of 0.5 g CER/g TS. It was observed that the extents of sludge hydrolysis and acidification had a strongly negative correlation with the organic binding iron (OBI) concentration. The presence of CER during anaerobic digestion favored Fe(III) reduction to Fe(II), and then further induced iron phase transformation, leading to the OBI formation from the released organic matters. Meanwhile, higher CER dosage resulted in higher P release efficiency and the maximum efficiency at 4 g CER/g TS was four times than that of the control. The reduction of BD-P, NaOH-P and HCl-P in solid phase contributed most P release into the supernatant. A new two-stage treatment process was further developed to immigrate the OBI formation and improve the carbon recovery efficiency. Through this process, approximately 45% of P was released, and 63% of carbon was recovered as methane from Fe-CEPS sludge via CER pretreatment.

Biological responses of alga Euglena gracilis to triclosan and galaxolide and the regulation of humic acid.

Although the toxicity of triclosan (TCS) and galaxolide (HHCB) in freshwater has been reported, little study is shed light on their molecular toxicity mechanism and the regulation of humic acid (HA). In this work, freshwater algae E. gracilis was selected to explore these processes, and the molecular toxicity mechanism was analyzed by metabolomics. TCS was more toxic to E. gracilis than HHCB at 1 d exposure with the EC50 value of 0.76 mg L-1, but HHCB showed a higher toxicity as the exposure time prolonged. HA could alleviate the toxicity of TCS and HHCB, mainly due to the inhibition of TCS uptake and oxidative stress, respectively. The perturbations on a number of antioxidant defense-related metabolites in response to TCS or HHCB also indicated oxidative stress was a main toxicity mechanism. However, the exposure to HHCB resulted in more pronounced perturbations in the purine metabolism than TCS, implying that HHCB may pose a genetic toxicity on algae. It may explain the higher toxicity of HHCB to algae as the exposure time increased. These findings provide a comprehensive understanding on the ecological risks of TCS or HHCB in natural waters.

Microplastics altered contaminant behavior and toxicity in natural waters.

Microplastics (MPs) have received an increasing attention because of their ubiquitous presence and aquatic toxicity associated with MPs and MP-bound contaminants in the natural water. This review is to critically examine the chemical additives leached from MPs, the altered contaminant behaviors and the resulting changes in their aquatic ecotoxicity. Available data suggest that heavy metals Zn, Cr, Pb, and Cd regulated and present in plastics at the sub-mg g-1 to mg g-1 level can leach a significant amount depending on MPs size, aging, pH, and salinity conditions. MP-bound organic contaminants are primarily additive-derived (e.g., brominated diphenyl ethers, nonylphenol, and bisphenol A) at the µg g-1 to mg g-1 level, and secondarily pyrogenic and legacy origins (e.g., PAHs and PCBs) in the range of ng g-1 and mg g-1. MPs tend to have higher but more variable sorption capacities for organic compounds than metals (1.77 ± 2.34 vs. 0.82 ± 0.94 mg g-1). MPs alter the behavior of heavy metals through the electrostatic interactions and surface complexation, while the transport of additive derived organic compounds are altered primarily through hydrophobic effect as supported by a positive correlation (R2 = 0.71) between the logarithmic MPs-adsorbed concentrations and octanol/water partition coefficients (KOW) of organic compounds. MPs constitute less than 0.01% of the total mass of aquatic particulates in typical waters, but play a discernible role in the local partitioning and long-distance movement of contaminants. MPs alone exert higher toxicity to invertebrates than algae; however, when MPs co-occur with pollutants, both synergistic and antagonistic toxicities are observed depending mainly on the ingestibility of MPs, the extent of sorption, MPs as a transport vector or a sink to scavenge pollutants. We finally suggest several key areas of future research directions and needed data concerning the role of MPs in mitigating pollutant leaching, transport and risk under conditions mimicking natural and polluted waters.

Highly efficient degradation of 2,2',4,4'-tetrabromodiphenyl ether through combining surfactant-assisted Zn0 reduction with subsequent Fenton oxidation.

2,2',4,4'-tetrabromodiphenyl ether (BDE47) was difficult to be rapidly degraded by common reductive debromination or oxidative decomposition. In this study, the debromination via surfactant-assisted zero valent zinc (Zn0) reduction and subsequent Fenton oxidation was combined to completely degrade BDE47. Firstly, Zn0 integrated with surfactants including cetyltrimethylammonium chloride (CTAC), polyethylene glycol dodecyl ether (Brij35), or 1-dodecanesulfonic acid sodium salt (SDS) were evaluated for their reactivity to debrominate BDE47. CTAC-assisted Zn0 system presented the highest removal efficiency of 98.6% for BDE47 (C0 = 5 mg/L) under the optimized conditions including 0.3 g/L of Zn0 particles and 0.05 g/L of CTAC at 25 °C and pH 4.0 during 1-h reaction. Subsequently, the debromination products as low-brominated BDEs were attacked by hydroxyl radicals (•OH) from Fenton reagent, which were decomposed into short-chain carboxylic acids and even mineralized within 2-h oxidation. In addition, HPLC, GC-MS, LC-MS/MS, and IC were employed to detect intermediates during this reaction/oxidation process and the pathways of debromination and oxidation were proposed according to carbon and bromine balance. The above combination achieved the complete degradation of BDE47 via a relative low-cost method to rapidly remove PBDEs, which provide a new approach for the effective treatment of halogenated organic pollutants.

Decomplexation removal of Ni(II)-citrate complexes through heterogeneous Fenton-like process using novel CuO-CeO2-CoOx composite nanocatalyst.

A novel CuO-CeO2-CoOx nanocatalyst was prepared for heterogeneous Fenton-like reaction to break the Ni2+-chelate into free Ni2+ in electroless nickel plating wastewater, followed by separation of Ni2+ in an insoluble form. The composite nanocatalysts prepared by co-precipitation method were characterized by XRD, TEM, and XPS, et al. Its catalytic activity as Fenton-like reagent was evaluated by the removal efficiency of Ni(II)-citrate after decomplexation and postprecipitation treatment. Subsequently, the effects of operating parameters on the decomplexation efficiency of the nanocatalysts were investigated including calcination temperature of catalysts, H2O2 concentration, catalyst dosage, initial pH and reaction temperature. Under optimized condition, the Ni(II)-citrate complexes (C0 = 1.0 mM) achieved the complete decomplexation (>99.9%) within 60-min reaction using 0.3 g/L of CuO-CeO2-CoOx calcined at 450 °C and 75 mM of H2O2 at pH 3.0 under 50 °C of reaction. Then, Ni2+ after decomplexation could be completely removed by the subsequent precipitation at pH 11.0. In addition, the life test of CuO-CeO2-CoOx catalyst indicated that, after recycled 10 times, its activity for decomplexation of Ni(II)-citrate decreased no more than 8%. As a result, this new heterogeneous Fenton-like process is promising for decomplexation and purification of electroless nickel plating wastewater as a sludge reduction technology.

Synchronous Hodgkin lymphoma and gastric adenocarcinoma: A rare case report and literature review.

Hodgkin lymphoma (HL) is a lymphoproliferative disease arising in the lymphoid tissue, which is characterized by Reed-Sternberg cells. Adenocarcinoma is the most frequent pathological type of stomach cancer. Improved survival in HL patients leads to the development of secondary malignancies. However, synchronous occurrence of these 2 malignancies is extremely rare. Here, we present a 45-year-old male complaining of a lymph node mass in the neck, without any abdominal symptoms, diagnosed as HL and gastric adenocarcinoma with hepatitis B carrier status. We treated the patient with 8 courses of pirarubicin bleomycin, vincristine, and dacarbazine (modified ABVD), and 4 courses of capecitabine therapy concurrently along with oral entecavir, as the patient survived longer than 20 months.The prognosis of multiple primary malignancies is poor because therapy is difficult, without a standard treatment. The frequency of multiple primary malignancies is increasing in recent years, and second malignancies in patients with cancer should be taken into consideration.

Prostate ultrasound imaging: evaluation of a two-step scoring system in the diagnosis of prostate cancer.

RATIONALE AND OBJECTIVES: This study aims to investigate the feasibility and performance of a two-step scoring system of ultrasound imaging in the diagnosis of prostate cancer. MATERIAL AND METHODS: 75 patients with 888 consecutive histopathologically verified lesions were included in this study. Step 1, an initial 5-point scoring system was developed based on conventional transrectal ultrasound (TRUS). Step 2, a final scoring system was evaluated according to contrast-enhanced transrectal ultrasound (CE-TRUS). Each lesion was evaluated using the two-step scoring system (step 1 + step 2) and compared with only using conventional TRUS (step 1). RESULTS: 888 lesions were histologically verified: 315 of them were prostate cancer from 46 patients and 573 were benign prostatic hypertrophy (BPH) from 29 patients. According to the two-step scoring system, 284 lesions were upgraded and 130 lesions were downgraded from step 1 to step 2 (this means using step 2 to assess the results by step 1). However, 96 cases were improperly upgraded after step 2 and 48 malignant lesions were still missed after step 2 as score-1. For the two-step scoring system, the sensitivity, specificity, and accuracy were 84.7%, 83.2%, and 83.7%, respectively, versus 22.8%, 96.6%, and 70.4%, respectively, for conventional TRUS. The area under the ROC curve (AUC) for lesion diagnosis was 0.799-0.952 for the two-step scoring system, versus 0.479-0.712 for conventional TRUS. The difference in the diagnostic accuracy of the two-step scoring system and conventional TRUS was statistically significant (P<0.0001). CONCLUSION: The two-step scoring system was straightforward to use and achieved a considerably accurate diagnostic performance for prostate cancer. The application of the two-step scoring system for prostate cancer is promising.

A New Method to Predict RNA Secondary Structure Based on RNA Folding Simulation.

RNA plays an important role in various biological processes; hence, it is essential when determining the functions of RNA to research its secondary structures. So far, the accuracy of RNA secondary structure prediction remains an area in need of improvement. This paper presents a novel method for predicting RNA secondary structure based on an RNA folding simulation model. This model assumes that the process of RNA folding from the random coil state to full structure is staged and in every stage of folding, the final state of an RNA is determined by the optimal combination of helical regions, which are urgently essential to dynamics of RNA formation. This paper proposes the First Large Free Energy Difference (FLED) in order to find the helical regions most urgently needed for optimal final state formation among all the possible helical regions. Tests on the datasets with known structures from public databases demonstrate that our method can outperform other current RNA secondary structure prediction methods in terms of prediction accuracy.

[Effects of arsenic trioxide combined with bortezomib on proliferation and apoptosis of K562 cells and their mechanism].

This study was aimed to investigate the effect of arsenic trioxide (As(2)O(3)) alone and in combination with bortezomib (Bor) on proliferation and apoptosis of leukemia cell line K562, and to analyze the potential mechanism. K562 cells were treated with different concentrations of As(2)O(3) or Bor (alone or combination) for 24, 48 h. MTT method was used to detect the cell proliferation. After K562 cells were treated with 0.5 µmol/L As(2)O(3) alone or in combination with 10 nmoL/L Bor, the apoptosis rate and cell cycle were measured by flow cytometry, and the activity of NF-κB was analyzed by SP immunohistochemistry. The results indicated that the different concentrations of As(2)O(3) and Bor could inhibit the K562 cell proliferation in a time- and dose-dependent manners (P < 0.05). The IC(50) of Bor and As(2)O(3) in 48 h were 20 nmol/L and 0.6 µmol/L respectively. When K562 cells were treated with As(2)O(3) or Bor alone for 24 h, the apoptotic rate of K562 cells increased, and the apoptotic rate in combination group was higher than that in As(2)O(3) or Bor group. The cells were apparently arrested in G(2)/M phase in Bor group and G(0)/G(1) phase in As(2)O(3) group. The activity of NF-κB decreased significantly in As(2)O(3) or Bor group (P < 0.05), this effect was most significant in the combination group (P < 0.01). It is concluded that both As(2)O(3) and Bor can inhibit the proliferation and induce apoptosis of K562 cells, a synergistic effect can be observed when a low dose of As(2)O(3) combined with low dose of Bor. The different cell cycle block site and the decrease of activity of NF-κB may be one of the mechanisms underlying their synergic effect.

[Effects of hyperbaric oxygenation combined with As(2)O(3) on proliferation of K562 cells and associated mechanism].

This study was aimed to explore the effects of hyperbaric oxygenation (HBO) alone or combined with As(2)O(3) on proliferation, apoptosis and expression of HIF-1a, VEGF, caspase-3 mRNA of K562 cells, and the molecular mechanism of As(2)O(3) enhancing the anti-leukemic effect of HBO so as to provide a scientific basis for clinical treatment of chronic myeloid leukemia. The effects of drugs on proliferation of K562 cells was assayed by MTT method, the apoptosis rate of K562 cells was detected by flow cytometry with Annexin V/PI double staining, the expressions of HIF-1a, VEGF, caspase-3 mRNA of K562 cells were determined by real-time quantitative PCR. The results showed that as compared with As(2)O(3) alone, HBO combined with As(2)O(3) could increase inhibitory rate of K562 cell proliferation, and enhance apoptotic effect, obviously down-regulate expressions of HIF-1a and VEGF mRNA, up-regulate expression of caspase-3 mRNA. The effect of HBO combined with As(2)O(3) was higher then effect of As(2)O(3) alone, and their effects were synergistic (P < 0.05). It is concluded that HBO combined with As(2)O(3) can increase the expression of caspase 3 mRNA and decrease the expression of HIF-1a and VEGF mRNA, which may be one of molecular mechanisms underlying their synergistic antileukemia efficacy.