RESUMO
Currently, multifunction has become an essential direction of personal protective equipment (PPE), but achieving the protective effect, flexibility, physiological comfort, and intelligent application of PPE simultaneously is still a challenge. Herein, inspired by the meso-structure of rhinoceros skin, a novel strategy is proposed by compounding an ammonium sulfate ((NH4)2SO4) solution soaked gelatin hydrogel with the high weight fraction and vertically interwoven Kevlar fibers to manufacture a flexible and wearable composite with enhanced puncture resistance and strain-sensing properties. After (NH4)2SO4 solution immersion, the hydrogel's tensile strength, toughness, and fracture strain were up to 3.77 MPa, 4.26 MJ/m3, and 305.19%, respectively, indicating superior mechanical properties. The Kevlar/hydrogel composites revealed excellent puncture resistance (quasi-static of 132.06 N and dynamic of 295.05 N), flexibility (138.13 mN/cm), and air and moisture permeability (17.83 mm/s and 2092.73 g m-2 day-1), demonstrating a favorable balance between the protective effect and wearing comfort even after 7 days of environmental exposure. Meanwhile, salt solution immersion endowed the composite with excellent strain-sensing properties at various bending angles (30-90°) and frequencies (0.25-1 Hz) and allowed it to monitor different human motions directly in real-time. The rhinoceros-skin-inspired Kevlar/hydrogel composites provide a simple and economical solution for antipuncture materials that combine high protective effects, a comfortable wearing experience, and good strain-sensing properties, promising multifunctional PPE in the future.
RESUMO
This study aimed to explore the molecular mechanism of neuronal cell adhesion molecule (NrCAM) by regulating Th17 cell differentiation in the pathogenesis of Graves' disease (GD). Naïve CD4+ T cells were isolated from peripheral blood mononuclear cells of GD patients and healthy control (HC) subjects. During the differentiation of CD4+ T cells into Th17 cells, NrCAM level in GD group was improved. Interference with NrCAM in CD4+ T cells of GD patients decreased the percentage of Th17 cells. NrCAM overexpression in CD4+ T cells of HC subjects increased the percentage of Th17 cells and upregulated p-IκBα, p50, p65, c-Rel protein expressions, and NF-κB inhibitor BAY11-7082 partially reversed NrCAM effect. NrCAM overexpression promoted the degradation of IκBα, and overexpression of small ubiquitin-related modifier 1 (SUMO-1) inhibited IκBα degradation. NrCAM overexpression reduced IκBα binding to SUMO-1. During Th17 cell differentiation in HC group, NrCAM overexpression increased IL-21 levels and secretion, and IL-21 neutralizing antibody reversed this effect. IL-21 level was decreased after p65 interference in CD4+ T cells of HC subjects. p65 interacts with IL-21 promoter region. In conclusion, NrCAM binds to SUMO-1 and increases phosphorylation of IκBα, leading to activation of NF-κB pathway, which promotes Th17 cell differentiation.
RESUMO
Effective treatment of myocardial ischemia-reperfusion (MIR) injury remains an unmet clinical need. Cardiomyocyte apoptosis is common at this stage and poses a significant risk. Corylin, a flavonoid compound extracted from Psoralea corylifolia L., has been shown to have anti-inflammatory, anticancer, and antiatherosclerotic properties. However, whether and how corylin affects MIR injury remain unclear. In this study, we explored the mechanism of corylin as a potent therapeutic agent for MI/R injury, using a left anterior descending (LAD) coronary artery ligation and oxygen-glucose deprivation and reperfusion (OGD/R) model in vivo and in vitro. TUNEL, Annexin-V/PI double staining,Ki67 immunohistochemistry, western blot analysis, and immunofluorescence were used to validate cell apoptosis level and Raf-1/ASK1 complex activity. The interaction between corylin and Raf-1/ASK1 complex was detected using molecular docking, corylin-Raf-1 binding assays, and coimmunoprecipitation (Co-IP). Moreover, TTC staining, echocardiography, HE staining, Masson trichrome staining and serological testing were performed to assess the cardioprotective effects of corylin in vivo. These findings showed that corylin reduces MIR injury-induced cardiomyocyte apoptosis and improves cardiac function. Mechanistically, corylin can interact with Raf-1 and promote the formation of the Raf-1/ASK1 complex, thus inhibiting cardiomyocyte apoptosis. In conclusion, our results demonstrate that corylin ameliorated cardiac dysfunction after MIR injury by reducing myocardial apoptosis.
RESUMO
BACKGROUND: Although B-mode imaging has been widely used in ultrasound-guided high-intensity focused ultrasound (HIFU) treatment, challenges remain in improving its quality and sensitivity for monitoring the thermal dose. Recently, quantitative ultrasound (QUS) imaging has been recognized with the potential to better sense the changes in the microstructure of ablated tissues. PURPOSE: This study proposed to use a QUS method called weighted ultrasound entropy (WUE) imaging to monitor the HIFU ablation. METHODS: Based on ex-vivo and in-vivo experiments, WUE images reflecting tissue changes during HIFU treatment under different acoustic power levels (174-308 W) were reconstructed with a newly established imaging framework. The performance of the proposed WUE imaging in the monitoring of HIFU treatment was compared with the corresponding B-mode images in terms of their contrast-to-noise ratios (CNRs) between the focal region and the background. RESULTS: It was found that HIFU irradiation with higher power generated larger WUE values in the focal region, and the bright spots grew in size as the acoustic sonication proceeded. Compared with the in-situ B-mode images, the WUE images had higher image quality in indicating lesion formation, with a 39.2%-53.4% improvement in the CNR at different stages. Meanwhile, a correlation (R = 0.84) between the damage area estimated in WUE images and that measured from the dissected ex-vivo tissue samples was found. CONCLUSIONS: WUE imaging is more sensitive and accurate than B-mode imaging in monitoring HIFU therapy. These findings suggest that WUE imaging could be a promising technique for assisting ultrasound-guided HIFU ablation.
RESUMO
Coiled-coil domain containing 88C (CCDC88C) is a component of non-canonical Wnt signaling, and its dysregulation causes colorectal cancer metastasis. Dysregulated expression of CCDC88C was observed in lymph node metastatic tumor tissues of breast cancer. However, the role of CCDC88C in breast cancer metastasis remains unclear. To address this, the stable BT549 and SKBR3 cell lines with CCDC88C overexpression or knockdown were developed. Loss/gain-of-function experiments suggested that CCDC88C drove breast cancer cell motility in vitro and lung and liver metastasis in vivo. We found that CCDC88C led to c-JUN-induced transcription activation. Overlapping genes were identified from the genes modulated by CCDC88C and c-JUN. CEMIP, one of these overlapping genes, has been confirmed to confer breast cancer metastasis. We found that CCDC88C regulated CEMIP mRNA levels via c-JUN and it exerted pro-metastatic capabilities in a CEMIP-dependent manner. Moreover, we identified the CCDC88C as a substrate of polypeptide N-acetylgalactosaminyltransferase 6 (GALNT6). GALNT6 was positively correlated with CCDC88C protein abundance in the normal breast and breast cancer tissues, indicating that GALNT6 might be associated with expression patterns of CCDC88C in breast cancer. Our data demonstrated that GALNT6 maintained CCDC88C stability by promoting its O-linked glycosylation, and the modification was critical for the pro-metastatic potential of CCDC88C. CCDC88C also could mediate the pro-metastatic potential of GALNT6 in breast cancer. Collectively, our findings uncover that CCDC88C may increase the risk of breast cancer metastasis and elucidate the underlying molecular mechanisms.
RESUMO
Purpose: To explore the early diagnostic value of superb microvascular imaging (SMI) features within the rotator cuff gap for frozen shoulder. Patients and Methods: This prospective study enrolled patients with acute early-stage frozen shoulder seeking treatment at Zhabei Central Hospital in Jing'an District, Shanghai, between July 2021 and December 2022 were enrolled in this study. Healthy controls were collected in a 1:1 ratio from the same hospital's physical examination center. All participants underwent SMI and power Doppler ultrasound (PDUS) of the rotator cuff gap. Results: The study included 79 patients with frozen shoulder and 77 healthy controls. Compared with the healthy control group, the patient group had a higher proportion of hypoechoic rotator cuff gap (81.0% vs 48.1%, P<0.001), a thicker coracohumeral ligament (2.60±1.01 vs 2.03±0.97, P<0.001), a thicker glenohumeral joint capsule (3.10±0.99 vs 2.46±1.17, P<0.001), and elevated blood grading using SMI (P<0.001) and PDUS (P=0.014). The highest area under the curve (AUC) was observed for SMI blood flow grading (AUC=0.824, 95% CI: 0.755-0.880, P<0.001), resulting in 82% sensitivity and 77% specificity when using a cutoff of 1. SMI blood flow grading was associated with external rotation <30° (P=0.007) and abduction <30° (P=0.013) but not with internal rotation <30° (P=0.630) or flexion <30° (P=0.562). Conclusion: The grading of SMI blood flow may emerge as a valuable predictive indicator for the early stages of frozen shoulder. This simple ultrasound technique holds the potential to enhance the diagnostic process, enabling early initiation of treatment and potentially improving patient outcomes.
RESUMO
Purpose: This study explored whether a free-breathing mean heart dose (FB-MHD) of 4 Gy is a reliable dose threshold for selecting left breast cancer patients after modified radical mastectomy suitable for deep inspiration breath-hold (DIBH) and developed anatomical indicators to predict FB-MHD for rapid selection. Materials and methods: Twenty-three patients with left breast cancer treated with DIBH were included to compare FB and DIBH plans. The patients were divided into the high-risk (FB-MHD ≥ 4 Gy) and low-risk (FB-MHD < 4 Gy) groups to compare dose difference, normal tissue complication probability (NTCP) and the DIBH benefits. Another 30 patients with FB only were included to analyze the capacity of distinguishing high-risk heart doses patients according to anatomical metrics, such as cardiac-to-chest Euclidean distance (CCED), cardiac-to-chest gap (CCG), and cardiac-to-chest combination (CCC). Results: All heart doses were significantly lower in patients with DIBH plans than in those with FB plans. Based on FB-MHD of 4 Gy cutoff, the heart dose, NTCP for cardiac death, and benefits from DIBH were significantly higher in the high-risk group than in the low-risk group. The CCED was a valid anatomical indicator with the largest area under the curve (AUC) of 0.83 and maintained 95 % sensitivity and 70 % specificity at the optimal cutoff value of 2.5 mm. Conclusions: An FB-MHD of 4 Gy could be used as an efficient dose threshold for selecting patients suitable for DIBH. The CCED may allow a reliable prediction of FB-MHD in left breast cancer patients at CT simulation.
RESUMO
BACKGROUND: To investigate the role of lncRNA LINC00665 in modulating ovarian cancer stemness and its influence on treatment resistance and cancer development. METHODS: We isolated ovarian cancer stem cells (OCSCs) from the COC1 cell line using a combination of chemotherapeutic agents and growth factors, and verified their stemness through western blotting and immunofluorescence for stem cell markers. Employing bioinformatics, we identified lncRNAs associated with ovarian cancer, with a focus on LINC00665 and its interaction with the CNBP mRNA. In situ hybridization, immunohistochemistry, and qPCR were utilized to examine their expression and localization, alongside functional assays to determine the effects of LINC00665 on CNBP. RESULTS: LINC00665 employs its Alu elements to interact with the 3'-UTR of CNBP mRNA, targeting it for degradation. This molecular crosstalk enhances stemness by promoting the STAU1-mediated decay of CNBP mRNA, thereby modulating the Wnt and Notch signaling cascades that are pivotal for maintaining CSC characteristics and driving tumor progression. These mechanistic insights were corroborated by a series of in vitro assays and validated in vivo using tumor xenograft models. Furthermore, we established a positive correlation between elevated CNBP levels and increased disease-free survival in patients with ovarian cancer, underscoring the prognostic value of CNBP in this context. CONCLUSIONS: lncRNA LINC00665 enhances stemness in ovarian cancer by mediating the degradation of CNBP mRNA, thereby identifying LINC00665 as a potential therapeutic target to counteract drug resistance and tumor recurrence associated with CSCs.
Assuntos
Proteínas do Citoesqueleto , Células-Tronco Neoplásicas , Neoplasias Ovarianas , RNA Longo não Codificante , Proteínas de Ligação a RNA , Animais , Feminino , Humanos , Camundongos , Linhagem Celular Tumoral , Proteínas do Citoesqueleto/genética , Proteínas do Citoesqueleto/metabolismo , Regulação Neoplásica da Expressão Gênica , Células-Tronco Neoplásicas/metabolismo , Neoplasias Ovarianas/genética , Neoplasias Ovarianas/metabolismo , Estabilidade de RNA , RNA Longo não Codificante/genética , RNA Longo não Codificante/metabolismo , RNA Mensageiro/genética , RNA Mensageiro/metabolismo , Proteínas de Ligação a RNA/genética , Proteínas de Ligação a RNA/metabolismoRESUMO
A pair of water-stable and highly porous homochiral fluorescent silver-organic framework enantiomers, namely, R-Ag-BPA-TPyPE (R-1) and S-Ag-BPA-TPyPE (S-1), had been prepared as enantioselective fluorescence sensors. Combining homochiral 1,1'-binaphthyl-2,2'-diyl hydrogen phosphate (BPA) with an AIE-based ligand tetrakis[4-(pyridin-4-yl)phenyl]ethene (TPyPE) in complexes R-1 and S-1 made them possess favorable circularly polarized luminescence (CPL) properties, and their CPL spectra were almost mirror images of each other. The luminescence dissymmetry factors (glum) are ±2.2 × 10-3 for R-1 and S-1, and the absolute fluorescence quantum yields (ΦFs) are 32.0% for R-1 and S-1, respectively. Complex R-1 could enantioselectively recognize two enantiomers of amino acids in water or DMF with high Stern-Volmer constants of 236-573 M-1 and enantioselectivity ratios of 1.40-1.78.
RESUMO
PURPOSE: This study aimed to determine whether radiation therapy plans created using an automatic delineating system and a RapidPlan (RP) module could rapidly and accurately predict heart doses and benefit from deep inspiratory breath-hold (DIBH) in patients with left breast cancer. METHODS AND MATERIALS: One hundred thirty-six clinically approved free breathing (FB) plans for patients with left breast cancer were included, defined as manual delineation-manual plan (MD-MP). A total of 104 of 136 plans were selected for RP model training. A total of 32 of 136 patients were automatically delineated by software, after which the RP generated plans, defined as automatic delineation-RapidPlan (AD-RP). In addition, 40 patients who used DIBH were included to analyze differences in heart benefits from DIBH. RESULTS: Two RP models were established for post-breast-conserving surgery (BCS) and post-modified radical mastectomy. There were no significant differences in most of the dosimetric parameters between the MD-MP and AD-RP. The heart doses of the 2 plans were strongly correlated in patients after BCS (0.80 ≤ r ≤ 0.88, P < .05) and moderately correlated in patients after postmodified radical mastectomy (0.46 ≤ r ≤ 0.58, P <.05). The RP model predicted the mean heart dose (MHD) within ± 59.67 cGy and ± 63.32 cGy for patients who underwent the 2 surgeries described above. The heart benefits from DIBH were significantly greater in patients with FB-MHD ≥ 4 Gy than in those with FB-MHD < 4 Gy. CONCLUSIONS: The combined automatic delineation RP model allows for the rapid and accurate prediction of heart dose under FB in patients with left breast cancer. FB-MHD ≥ 4 Gy can be used as a dose threshold to select patients suitable for DIBH.
RESUMO
Without light at night, the system for photocatalytic degradation of refractory organic pollutants in aquatic environments based on free radicals will fall into a dormant state. Hence, a round-the-clock photocatalyst (CCN@SMSED) was prepared by in situ growth of cyanide-deficient g-C3N4 on the surface of Sr2MgSi2O7:Eu2+,Dy3+ through a simple calcination method. The CCN@SMSED exhibits an outstanding oxidative degradation ability for refractory tetracycline (TC) in water under both light and dark conditions, which is attributed to the synergistic effect of free radical (â¢O2- and â¢OH) and non-radical (h+ and 1O2). Electrochemical analyses further indicate that direct electron transfer (DET) is also one of the reasons for the efficient degradation of TC. Remarkably, the continuous working time of the round-the-clock photocatalyst in a dark environment was estimated for the first time (about 2.5 h in this system). The degradation pathways of TC mainly include demethylation, ring opening, deamination and dehydration, and the growth of Staphylococcus aureus shows that the process is biosafe. More importantly, CCN@SMSED holds significant promise for practical application due to its low energy consumption and suitability for removing TC from a variety of complex water bodies. This work provides an energy consumption reference for the practical application of round-the-clock photocatalytic degradation of organic pollutants.
Assuntos
Tetraciclina , Poluentes Químicos da Água , Tetraciclina/química , Poluentes Químicos da Água/química , Catálise , Fotólise , Grafite , Nitrilas , Compostos de NitrogênioRESUMO
Kidney Clear Cell Carcinoma (KIRC), the predominant form of kidney cancer, exhibits a diverse therapeutic response to Immune Checkpoint Inhibitors (ICIs), highlighting the need for predictive models of ICI efficacy. Our study has constructed a prognostic model based on 13 types of Programmed Cell Death (PCD), which are intertwined with tumor progression and the immune microenvironment. Validated by analyses of comprehensive datasets, this model identifies seven key PCD genes that delineate two subtypes with distinct immune profiles and sensitivities to anti-PD-1 therapy. The high-PCD group demonstrates a more immune-suppressive environment, while the low-PCD group shows better responses to PD-1 treatment. In particular, TOP2A emerged as crucial, with its inhibition markedly reducing KIRC cell growth and mobility. These findings underscore the relevance of PCDs in predicting KIRC outcomes and immunotherapy response, with implications for enhancing clinical decision-making.
RESUMO
BACKGROUND: Napping is garnering increased attention as a strategy for adults to sustain alertness and alleviate stress in contemporary society. The nuances of napping habits are emerging as an independent factor influencing the extent of individual benefits. This study aimed to demonstrate the long-term benefits of napping and explore the impact of napping habits on individual alertness, as well as whether this effect was correlated with cortisol levels. METHODS: The study involved 80 healthy adults categorized into two groups based on self-reported napping habits: habitual nappers (n = 49) and non-habitual nappers (n = 31). Karolinska Sleepiness Scale (KSS), psychomotor vigilance task (PVT), and saliva collection were performed every 30 min within 90 min in the absence of napping during the afternoon dip. The measurements were analyzed using repeated measures ANOVA and Pearson correlation analyses. RESULTS: There was an interaction between groups and time in reaction speed and lapse number of PVT and cortisol (all p < 0.05). Post hoc analysis found that habitual nappers maintained higher objective alertness and experienced more significant increases in cortisol over time (all p < 0.05). The cortisol levels at sleepiness time were negatively associated with the slowest 10 % reaction speed of PVT in non-habitual nappers (r = -0.409, p = 0.022). CONCLUSION: Under the premise of mitigating the impacts of acute nap deprivation on sleep homeostasis and rhythm, napping habits emerge as a potential factor influencing the ability of individuals to sustain heightened alertness.
Assuntos
Hábitos , Hidrocortisona , Desempenho Psicomotor , Saliva , Sono , Humanos , Hidrocortisona/análise , Hidrocortisona/metabolismo , Masculino , Feminino , Sono/fisiologia , Saliva/química , Adulto , Desempenho Psicomotor/fisiologia , Tempo de Reação/fisiologia , Adulto Jovem , Atenção/fisiologia , Vigília/fisiologia , Fatores de Tempo , AutorrelatoRESUMO
Objective To establish a model for predicting the growth of pulmonary ground-glass nodules (GGN) based on the clinical visualization parameters extracted by the 3D reconstruction technique and to verify the prediction performance of the model. Methods A retrospective analysis was carried out for 354 cases of pulmonary GGN followed up regularly in the outpatient of pulmonary nodules in Zhoushan Hospital of Zhejiang Province from March 2015 to December 2022.The semi-automatic segmentation method of 3D Slicer was employed to extract the quantitative imaging features of nodules.According to the follow-up results,the nodules were classified into a resting group and a growing group.Furthermore,the nodules were classified into a training set and a test set by the simple random method at a ratio of 7â¶3.Clinical and imaging parameters were used to establish a prediction model,and the prediction performance of the model was tested on the validation set. Results A total of 119 males and 235 females were included,with a median age of 55.0 (47.0,63.0) years and the mean follow-up of (48.4±16.3) months.There were 247 cases in the training set and 107 cases in the test set.The binary Logistic regression analysis showed that age (95%CI=1.010-1.092,P=0.015) and mass (95%CI=1.002-1.067,P=0.035) were independent predictors of nodular growth.The mass (M) of nodules was calculated according to the formula M=V×(CTmean+1000)×0.001 (where V is the volume,V=3/4πR3,R:radius).Therefore,the logit prediction model was established as ln[P/(1-P)]=-1.300+0.043×age+0.257×two-dimensional diameter+0.007×CTmean.The Hosmer-Lemeshow goodness of fit test was performed to test the fitting degree of the model for the measured data in the validation set (χ2=4.515,P=0.808).The check plot was established for the prediction model,which showed the area under receiver-operating characteristic curve being 0.702. Conclusions The results of this study indicate that patient age and nodule mass are independent risk factors for promoting the growth of pulmonary GGN.A model for predicting the growth possibility of GGN is established and evaluated,which provides a basis for the formulation of GGN management strategies.
Assuntos
Neoplasias Pulmonares , Nódulo Pulmonar Solitário , Humanos , Pessoa de Meia-Idade , Feminino , Masculino , Estudos Retrospectivos , Neoplasias Pulmonares/diagnóstico por imagem , Neoplasias Pulmonares/patologia , Nódulo Pulmonar Solitário/diagnóstico por imagem , Nódulo Pulmonar Solitário/patologia , Tomografia Computadorizada por Raios X/métodos , Nódulos Pulmonares Múltiplos/diagnóstico por imagem , Nódulos Pulmonares Múltiplos/patologia , Imageamento Tridimensional/métodos , Idoso , AdultoRESUMO
Designing and developing high-performance shielding materials against electromagnetic interference is of utmost importance due to the rapid advancement of wireless telecommunication technologies. Such materials hold both fundamental and technological significance. A three-stage process is presented for creating ultralight, flexible aerogels from biomass to shield against electromagnetic interference. Collagen fibers sourced from leather solid waste are used for: (i) freeze-drying preparation of collagen fibers/poly(vinyl alcohol) (PVA) aerogels, (ii) adsorption of silver nanowires (AgNWs) onto collagen fiber/PVA aerogels, and (iii) Hydrophobic modification of collagen fiber/PVA/AgNWs aerogels with 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane (POTS). Scanning electron microscopy studies reveal that an interweaving of AgNWs and collagen fiber/PVA porous network has formed a conductive network, exhibiting an electrical conductivity of 103 S·m-1. The electromagnetic interference shielding effectiveness reached more than 62 dB, while the density was merely 5.8 mg/cm3. The collagen fiber/PVA/AgNWs/POTS aerogel displayed an even better electromagnetic shielding efficiency of 73 dB and water contact angle of 147°. The study results emphasize the distinctive capacity of leather solid waste to generate cost-effective, ecofriendly, and highly efficient electromagnetic interference shielding materials.
RESUMO
Background: Investigations assessing the value of metagenomic next-generation sequencing (mNGS) for distinguish Aspergillus infection from colonization are currently insufficient. Methods: The performance of mNGS in distinguishing Aspergillus infection from colonization, along with the differences in patients' characteristics, antibiotic adjustment, and lung microbiota, were analyzed. Results: The abundance of Aspergillus significantly differed between patients with Aspergillus infection (n=36) and colonization (n=32) (P < 0.0001). Receiver operating characteristic (ROC) curve result for bronchoalveolar lavage fluid (BALF) mNGS indicated an area under the curve of 0.894 (95%CI: 0.811-0.976), with an optimal threshold value of 23 for discriminating between Aspergillus infection and colonization. The infection group exhibited a higher proportion of antibiotic adjustments in comparison to the colonization group (50% vs. 12.5%, P = 0.001), with antibiotic escalation being more dominant. Age, length of hospital stay, hemoglobin, cough and chest distress were significantly positively correlated with Aspergillus infection. The abundance of A. fumigatus and Epstein-Barr virus (EBV) significantly increased in the infection group, whereas the colonization group exhibited higher abundance of A. niger. Conclusion: BALF mNGS is a valuable tool for differentiating between colonization and infection of Aspergillus. Variations in patients' age, length of hospital stay, hemoglobin, cough and chest distress are observable between patients with Aspergillus infection and colonization.
Assuntos
Aspergilose , Infecções por Vírus Epstein-Barr , Pneumonia , Humanos , Herpesvirus Humano 4 , Aspergillus/genética , Tosse , Líquido da Lavagem Broncoalveolar , Sequenciamento de Nucleotídeos em Larga Escala , Antibacterianos , Pulmão , Hemoglobinas , Sensibilidade e Especificidade , Estudos RetrospectivosRESUMO
As important components of soluble microbial products in water, nucleobases have attracted much attention due to the high toxicity of their direct aromatic halogenated disinfection by-products (AH-DBPs) during chlorination. However, multiple halogenation sites of AH-DBPs pose challenges to identify them. In this study, reaction sites of pyrimidine bases and nucleosides during chlorination were investigated by quantum chemical computational method. The results indicate that the anion salt forms play key roles in chlorination of uracil, thymine, and their nucleosides, while neutral forms make predominant contributions to cytosine and cytidine. In view of both kinetics and thermodynamics, C5 is the most reactive site for uracil and thymine, N3/C5 and N3 for respective uridine and thymidine, N1/C5/N4 and N4 for respective cytosine and cytidine, whose estimated apparent rate constants kobs-est of â¼103, 103/102, 106/102/104, and 103 M-1 s-1, respectively, in consistent with the known experimental results. C6 in all pyrimidine compounds is hardly attacked by Cl+ in HOCl ascribed to its positive charge, but readily attacked by OHâ¾ in hydrolysis and the N1=C6 bond was found to possess the highest reactivity in hydrolysis among all double bonds. In addition, the structure-kinetic reactivity relationship study reveals a relatively strong correlation between lgkobs-est and APT charge in all pyrimidine compounds rather than FED2 (HOMO). The results are helpful to further understand the reactivity of various reaction sites in aromatic compounds during chlorination.