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1.
J Environ Sci (China) ; 150: 349-361, 2025 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-39306410

RESUMO

The capability of traditional ligand in countering rapid passivation on nanoscale zero-valent iron (nZVI) surface is inadequate, and the precise electron transfer mechanism remains elusive. In this study, we reported that myo-inositol hexakisphosphate (IHP), a redox-inactive organophosphorus in soil, could highly enhance Cr(VI) reduction and immobilization in comparison with typical ligands (TPP, EDTA, oxalate and phosphate). And the effects of IHP concentration, Cr(VI) concentration and initial pH were systematically investigated. Cr K-edge XANES and XPS analysis revealed that Cr(III) was the exclusive form in solid products regardless of IHP existence. Results of ATR-FTIR and FESEM inferred that IHP was adsorbed on nZVI surface via inner-sphere complexation, thus averting encapsulation of [Fe, Cr](OH)3 coprecipitate and impeding solid particles agglomeration. Additionally, IHP expedited the production of surface-bound Fe(II), primarily attributable to the interaction between nZVI and oxygen. These surface-bound Fe(II) species played a pivotal role in Cr(VI) reduction. Electrochemical analysis unveiled that IHP lowered redox potential of Fe(III)/Fe(II), thereby facilitating reaction between Fe(II) and Cr(VI), whereas inhibited direct electron transfer from nZVI core to Cr(VI). Our findings proposed a novel potential ligand for alleviating nZVI passivation in Cr(VI) removal and deepened our understanding in the process of electron transfer.


Assuntos
Cromo , Ferro , Cromo/química , Ferro/química , Ácido Fítico/química , Oxirredução , Modelos Químicos , Transporte de Elétrons , Poluentes do Solo/química , Adsorção
2.
J Int Med Res ; 52(9): 3000605241238689, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39291412

RESUMO

OBJECTIVE: Combined small cell lung cancer (CSCLC) with distant metastasis (DM) is an aggressive disease with a poor prognosis. Effective nomograms are needed to predict DM and early death in patients with CSCLC and DM. METHODS: This retrospective study included patients with CSCLC from the Surveillance, Epidemiology, and End Results database between 2004 and 2015. Risk factors for DM and early death were analyzed by univariate and multivariate logistic regression. Nomograms were constructed based on the results in a training cohort and confirmed in a validation cohort, and their performances were assessed by concordance index (C-index), receiver operating characteristic curve (ROC), calibration curve, and decision curve analysis (DCA). RESULTS: A total of 788 patients with CSCLC were selected, including 364 patients with metastatic CSCLC. Sex, tumor site, T stage, and N stage were independent risk factors for DM, while age, surgery, chemotherapy, and liver metastasis were independent risk factors for early death. C-index, ROC, calibration, and DCA curve analyses all showed good predictive performances for both nomograms. CONCLUSIONS: These nomograms could reliably predict DM risk in CSCLC patients and early death in CSCLC patients with DM, and may thus help clinicians to assess these risks and implement individualized therapies.


Assuntos
Neoplasias Pulmonares , Nomogramas , Curva ROC , Carcinoma de Pequenas Células do Pulmão , Humanos , Masculino , Feminino , Neoplasias Pulmonares/mortalidade , Neoplasias Pulmonares/patologia , Neoplasias Pulmonares/diagnóstico , Fatores de Risco , Pessoa de Meia-Idade , Idoso , Carcinoma de Pequenas Células do Pulmão/mortalidade , Carcinoma de Pequenas Células do Pulmão/patologia , Carcinoma de Pequenas Células do Pulmão/diagnóstico , Estudos Retrospectivos , Estadiamento de Neoplasias , Programa de SEER , Metástase Neoplásica , Prognóstico , Adulto , Neoplasias Hepáticas/mortalidade , Neoplasias Hepáticas/secundário , Neoplasias Hepáticas/diagnóstico
3.
Biosens Bioelectron ; 266: 116727, 2024 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-39232433

RESUMO

The isolation and identification of pathogenic bacteria from a variety of samples are critical for controlling bacterial infection-related health problems. The conventional methods, such as plate counting and polymerase chain reaction-based approaches, tend to be time-consuming and reliant on specific instruments, severely limiting the effective identification of these pathogens. In this study, we employed the specificity of the cell wall-binding (CBD) domain of the Staphylococcus aureus bacteriophage 80 alpha (80α) endolysin towards the host bacteria for isolation. Amidase 3-CBD conjugated magnetic beads successfully isolated as few as 1 × 102 CFU/mL of S. aureus cells from milk, blood, and saliva. The cell wall hydrolyzing activity of 80α endolysin promoted the genomic DNA extraction efficiency by 12.7 folds on average, compared to the commercial bacterial genomic DNA extraction kit. Then, recombinase polymerase amplification (RPA) was exploited to amplify the nuc gene of S. aureus from the extracted DNA at 37 °C for 30 min. The RPA product activated Cas12a endonuclease activity to cleave fluorescently labeled ssDNA probes. We then converted the generated signal into a fluorescent readout, detectable by either the naked eye or a portable, self-assembled instrument with ultrasensitivity. The entire procedure, from isolation to identification, can be completed within 2 h. The simplicity and sensitivity of the method developed in this study make it of great application value in S. aureus detection, especially in areas with limited resource supply.


Assuntos
Técnicas Biossensoriais , Endopeptidases , Staphylococcus aureus , Staphylococcus aureus/isolamento & purificação , Staphylococcus aureus/virologia , Técnicas Biossensoriais/métodos , Endopeptidases/química , Endopeptidases/isolamento & purificação , Endopeptidases/genética , Bacteriófagos/química , Bacteriófagos/genética , Bacteriófagos/isolamento & purificação , Humanos , Fagos de Staphylococcus/genética , Fagos de Staphylococcus/química , Fagos de Staphylococcus/isolamento & purificação , Animais , Técnicas de Amplificação de Ácido Nucleico/métodos , Infecções Estafilocócicas/microbiologia , DNA Bacteriano/genética , DNA Bacteriano/isolamento & purificação , Nuclease do Micrococo/química , Nuclease do Micrococo/metabolismo , Nuclease do Micrococo/genética , Proteínas Virais/química , Proteínas Virais/metabolismo
4.
Nat Nanotechnol ; 2024 Sep 09.
Artigo em Inglês | MEDLINE | ID: mdl-39251863

RESUMO

A photonic bandgap is a range of wavelengths wherein light is forbidden from entering a photonic crystal, similar to the electronic bandgap in semiconductors. Fabricating photonic crystals with a complete photonic bandgap in the visible spectrum presents at least two important challenges: achieving a material refractive index > ~2 and a three-dimensional patterning resolution better than ~280 nm (lattice constant of 400 nm). Here we show an approach to overcome such limitations using additive manufacturing, thus realizing high-quality, high-refractive index photonic crystals with size-tunable bandgaps across the visible spectrum. We develop a titanium ion-doped resin (Ti-Nano) for high-resolution printing by two-photon polymerization lithography. After printing, the structures are heat-treated in air to induce lattice shrinkage and produce titania nanostructures. We attain three-dimensional photonic crystals with patterning resolution as high as 180 nm and refractive index of 2.4-2.6. Optical characterization reveals ~100% reflectance within the photonic crystal bandgap in the visible range. Finally, we show capabilities in defining local defects and demonstrate proof-of-principle applications in spectrally selective perfect reflectors and chiral light discriminators.

5.
Heliyon ; 10(17): e36787, 2024 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-39286173

RESUMO

Objective: This study investigated the clinical effects and applicability of minimally invasive impacted teeth extraction using digital robots. Methods: A marker was bonded to the non-surgical area before surgery. A Cone-Beam Computed Tomography (CBCT) scan was obtained and uploaded to the robot software to determine the drilling position of the ring drill. During the surgery, the robot arm automatically navigated to a predetermined position, and the ring drill removed part of the bone tissue and exposed and extracted the impacted teeth. Finally, the surgeon tightly sutured the wounds to the surgical area. Results: Three minimally invasive extractions of impacted teeth with robotic assistance were performed without complications. The surgical area showed good healing during the one-month follow-up examination. Conclusions: Digital robot-assisted minimally invasive extraction of impacted teeth is a highly feasible clinical procedure as it minimises trauma to the surgical area and protects the surrounding blood vessels and nerve bundles, making it a safe and valuable technique with significant potential for clinical application.

6.
Adv Sci (Weinh) ; : e2407069, 2024 Sep 03.
Artigo em Inglês | MEDLINE | ID: mdl-39225567

RESUMO

Lipid metabolism reprogramming stands as a fundamental hallmark of cancer cells. Unraveling the core regulators of lipid biosynthesis holds the potential to find promising therapeutic targets in pancreatic ductal adenocarcinoma (PDAC). Here, it is demonstrated that platelet-derived growth factor C (PDGFC) orchestrated lipid metabolism, thereby facilitated the malignant progression of PDAC. Expression of PDGFC is upregulated in PDAC cohorts and is corelated with a poor prognosis. Aberrantly high expression of PDGFC promoted proliferation and metastasis of PDAC both in vitro and in vivo. Mechanistically, PDGFC accelerated the malignant progression of PDAC by upregulating fatty acid accumulation through sterol regulatory element-binding protein 1 (SREBP1), a key transcription factor in lipid metabolism. Remarkably, Betulin, an inhibitor of SREBP1, demonstrated the capability to inhibit proliferation and metastasis of PDAC cell lines, along with attenuating the process of liver metastasis in vivo. Overall, the study underscores the pivotal role of PDGFC-mediated lipid metabolism in PDAC progression, suggesting PDGFC as a potential biomarker for PDAC metastasis. Targeting PDGFC-induced lipid metabolism emerges as a promising therapeutic strategy for metastatic PDAC, with the potential to improve clinical outcomes.

7.
BMC Pulm Med ; 24(1): 443, 2024 Sep 11.
Artigo em Inglês | MEDLINE | ID: mdl-39261827

RESUMO

BACKGROUND: Pulmonary fibrosis (PF) is an aging-related progressive lung disorder. The aged lung undergoes functional and structural changes termed immunosenescence and inflammaging, which facilitate the occurrence of fibrosis. Interleukin-10 (IL-10) is a potent anti-inflammatory and immunoregulatory cytokine, yet it remains unclear how IL-10 deficiency-induced immunosenescence participates in the development of PF. METHODS: Firstly we evaluated the susceptibility to fibrosis and IL-10 expression in aged mice. Then 13-month-old wild-type (WT) and IL-10 knockout (KO) mice were subjected to bleomycin(BLM) and analyzed senescence-related markers by PCR, western blot and immunohistochemistry staining of p16, p21, p53, as well as DHE and SA-ß-gal staining. We further compared 18-month-old WT mice with 13-month-old IL-10KO mice to assess aging-associated cell senescence and inflamation infiltration in both lung and BALF. Moreover, proliferation and apoptosis of alveolar type 2 cells(AT2) were evaluated by FCM, immunofluorescence, TUNEL staining, and TEM analysis. Recombinant IL-10 (rIL-10) was also administered intratracheally to evaluate its therapeutic potential and related mechanism. For the in vitro experiments, 10-week-old naïve pramily lung fibroblasts(PLFs) were treated with the culture medium of 13-month PLFs derived from WT, IL-10KO, or IL-10KO + rIL-10 respectively, and examined the secretion of senescence-associated secretory phenotype (SASP) factors and related pathways. RESULTS: The aged mice displayed increased susceptibility to fibrosis and decreased IL-10 expression. The 13-month-old IL-10KO mice exhibited significant exacerbation of cell senescence compared to their contemporary WT mice, and even more severe epithelial-mesenchymal transition (EMT) than that of 18 month WT mice. These IL-10 deficient mice showed heightened inflammatory responses and accelerated PF progression. Intratracheal administration of rIL-10 reduced lung CD45 + cell infiltration by 15%, including a 6% reduction in granulocytes and a 10% reduction in macrophages, and increased the proportion of AT2 cells by approximately 8%. Additionally, rIL-10 significantly decreased α-SMA and collagen deposition, and reduced the expression of senescence proteins p16 and p21 by 50% in these mice. In vitro analysis revealed that conditioned media from IL-10 deficient mice promoted SASP secretion and upregulated senescence genes in naïve lung fibroblasts, which was mitigated by rIL-10 treatment. Mechanistically, rIL-10 inhibited TGF-ß-Smad2/3 and PTEN/PI3K/AKT/ERK pathways, thereby suppressing senescence and fibrosis-related proteins. CONCLUSIONS: IL-10 deficiency in aged mice leads to accelerated cell senescence and exacerbated fibrosis, with IL-10KO-PLFs displaying increased SASP secretion. Recombinant IL-10 treatment effectively mitigates these effects, suggesting its potential as a therapeutic target for PF.


Assuntos
Bleomicina , Senescência Celular , Interleucina-10 , Camundongos Knockout , PTEN Fosfo-Hidrolase , Proteínas Proto-Oncogênicas c-akt , Fibrose Pulmonar , Animais , Interleucina-10/metabolismo , Interleucina-10/genética , Camundongos , Fibrose Pulmonar/patologia , Fibrose Pulmonar/metabolismo , Proteínas Proto-Oncogênicas c-akt/metabolismo , PTEN Fosfo-Hidrolase/genética , PTEN Fosfo-Hidrolase/metabolismo , Camundongos Endogâmicos C57BL , Sistema de Sinalização das MAP Quinases , Apoptose , Pulmão/patologia , Pulmão/metabolismo , Masculino , Células Epiteliais Alveolares/metabolismo , Células Epiteliais Alveolares/patologia , Modelos Animais de Doenças , Proliferação de Células , Envelhecimento , Transdução de Sinais
8.
Int J Radiat Biol ; 100(10): 1493-1504, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-39166981

RESUMO

PURPOSE: Radiation cystitis (RC) is a complex and common complication after radiotherapy for pelvic cancer. Icariside II (ICAII) is a flavonoid compound extracted from Epimedium, a traditional Chinese medicine, with various pharmacological activities. The aim of the present study was to investigate the cysto-protective effects of ICAII in RC rats and its possible mechanisms. MATERIALS AND METHODS: A rat model of induced radiation cystitis using pelvic X-ray irradiation was used, and bladder function was assessed by bladder volume and bladder leakage point pressure (LPP) after ICAII treatment. HE and Masson stains were used to assess the histopathological changes in the bladder. IL-6, TNF-α, IL-10, IL-4 and IL-1ß were measured by ELISA to assess the level of inflammation. The gene-level changes in ICAII-treated RC were observed by transcriptome sequencing, and then the potential targets of action and biological mechanisms were explored by PPI, GO and KEGG enrichment analysis of the differentially expressed genes. Finally, the predicted targets of action were experimentally validated using immunohistochemistry, RT-qPCR, molecular docking and CETSA. RESULTS: ICAII significantly increased bladder volume and the LPP, ameliorated pathological damage to bladder tissues, decreased the levels of IL-6, TNF-α, and IL-1ß, and increased the levels of IL-10 and IL-4 in radiation-injured rats. A total of 90 differentially expressed genes were obtained by transcriptome sequencing, and PPI analysis identified H3F3C, ISG15, SPP1, and LCN2 as possible potential targets of action. GO and KEGG analyses revealed that these differentially expressed genes were mainly enriched in the pathways metabolism of xenobiotics by cytochrome P450, arachidonic acid metabolism, Staphylococcus aureus infection and chemical carcinogenesis - reactive oxygen species. Experimental validation showed that ICAII could significantly increase the expression of H3F3C and ISG15 and inhibit the expression of SPP1 and LCN2. ICAII binds well to H3F3C, ISG15, SPP1 and LCN2, with the best binding ability to H3F3C. Furthermore, ICAII inhibited the protein degradation of H3F3C in bladder epithelial cells. CONCLUSIONS: ICAII may alleviate the bladder inflammatory response and inhibit the fibrosis process of bladder tissues through the regulation of H3F3C, ISG15, SPP1, and LCN2 targets and has a protective effect on the bladder of radioinjured rats. In particular, H3F3C may be one of the most promising therapeutic targets.


Assuntos
Cistite , Flavonoides , Bexiga Urinária , Animais , Ratos , Cistite/induzido quimicamente , Cistite/metabolismo , Cistite/prevenção & controle , Bexiga Urinária/efeitos dos fármacos , Bexiga Urinária/efeitos da radiação , Bexiga Urinária/patologia , Bexiga Urinária/metabolismo , Flavonoides/farmacologia , Ratos Sprague-Dawley , Feminino , Transcriptoma/efeitos dos fármacos , Protetores contra Radiação/farmacologia , Modelos Animais de Doenças , Citocinas/metabolismo , Simulação de Acoplamento Molecular
9.
J Inorg Biochem ; 261: 112706, 2024 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-39197384

RESUMO

In this study, the ligand EIPP (5-ethoxy-2-(1H-imidazo[4,5-f] [1,10] phenanthrolin-2-yl)phenol) and [Ir(ppy)2(EIPP)](PF6)] (5a, ppy = 2-phenylpyridine) and [Ir(piq)2(EIPP)](PF6)] (5b, piq = 1-phenylisoquinoline) were synthesized and they were entrapped into liposomes to produce 5alipo and 5blipo. 5a and 5b were characterized via HRMS, NMR, UV-vis and IR. The cytotoxicity of 5a, 5b, 5alipo and 5blipo on cancer and non-cancer cells was estimated using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT). MTT assay demonstrated that 5a and 5b did not show any significant cellular activity but their liposome-encapsulated 5alipo and 5blipo had significant toxic effects. The mechanism of 5alipo, 5blipo-inducing apoptosis was explored by studying cellular uptake, mitochondrial localization, mitochondrial membrane potential, cytochrome C, glutathione (GSH), malondialdehyde (MDA) and protein immunoblotting. The results demonstrated that 5alipo and 5blipo caused a release of cytochrome C, downregulated the expression of Bcl-2, upregulated the expression of BAX, activated caspase 3, and downregulated PARP expression. It was shown that 5alipo and 5blipo could inhibit cancer cell proliferation in G2/M phase by regulating p53 and p21 proteins. Additionally, 5alipo and 5blipo induced autophagy through an adjustment from LC3-I to LC3-II and caused ferroptosis. The in vivo antitumor activity of 5alipo was examined in detail.


Assuntos
Antineoplásicos , Apoptose , Complexos de Coordenação , Irídio , Lipossomos , Humanos , Irídio/química , Irídio/farmacologia , Antineoplásicos/farmacologia , Antineoplásicos/química , Antineoplásicos/síntese química , Apoptose/efeitos dos fármacos , Animais , Complexos de Coordenação/farmacologia , Complexos de Coordenação/química , Complexos de Coordenação/síntese química , Camundongos , Linhagem Celular Tumoral , Proliferação de Células/efeitos dos fármacos
11.
Sci Rep ; 14(1): 18279, 2024 08 07.
Artigo em Inglês | MEDLINE | ID: mdl-39112553

RESUMO

Acute pancreatitis (AP) is a common disease caused by a variety of causes. Is uric acid associated with the onset of AP? The objective of this study was to assess whether uric acid concentration in AP patients was higher than that in healthy population, and whether there were associations between uric acid concentration and serological indicators related to AP. A total of 205 AP patients were included in this study. Two hundred and five people who underwent physical examination in our hospital were randomly selected as controls. We analyzed whether there was difference in uric acid concentrations between the two groups. If the difference was statistically significant, the correlations between uric acid concentration and serological indicators in AP patients was further analyzed. There was significant difference in uric acid concentration (P < 0.001) between AP patients and healthy population. Serum uric acid concentration in AP group was significantly higher than that in control group. Two hundred and five AP patients were divided into mild AP group and non-mild AP group. There was no statistically significant difference in uric acid concentration between the two groups (P = 0.176). There was a low linear correlation between serum uric acid concentration and triglyceride level (r = 0.316, P < 0.001). But there was no linear correlation between serum uric acid concentration and hypersensitive C-reactive protein (r = 0.126, P = 0.072), white blood cell (r = 0.192, P = 0.006), albumin (r = 0.183, P = 0.009), total cholesterol concentration (r = 0.133, P = 0.058), fasting blood-glucose (r = 0.133, P = 0.058) and blood calcium (r = 0.155, P = 0.026). Uric acid concentration in patients with AP was significantly higher than healthy population. There was correlation between uric acid concentration and triglyceride in AP patients.


Assuntos
Pancreatite , Ácido Úrico , Humanos , Ácido Úrico/sangue , Masculino , Feminino , Pessoa de Meia-Idade , Pancreatite/sangue , Pancreatite/diagnóstico , Adulto , Estudos de Casos e Controles , Proteína C-Reativa/metabolismo , Proteína C-Reativa/análise , Idoso , Triglicerídeos/sangue , Doença Aguda , Biomarcadores/sangue
12.
Environ Sci Technol ; 2024 Jul 18.
Artigo em Inglês | MEDLINE | ID: mdl-39021234

RESUMO

Cadmium (Cd) geochemical behavior is strongly influenced by its adsorption onto natural phyllomanganates, which contain both layer edge sites and vacancies; however, Cd isotope fractionation mechanisms at these sites have not yet been addressed. In the present work, Cd isotope fractionation during adsorption onto hexagonal (containing both types of sites) and triclinic birnessite (almost only edge sites) was investigated using a combination of batch adsorption experiments, extended X-ray absorption fine structure (EXAFS) spectroscopy, surface complexation modeling, and density functional theory (DFT) calculations. Light Cd isotopes are preferentially enriched on solid surfaces, and the isotope fractionation induced by Cd2+ adsorption on edge sites (Δ114/110Cdedge-solution = -1.54 ± 0.11‰) is smaller than that on vacancies (Δ114/110Cdvacancy-solution = -0.71 ± 0.21‰), independent of surface coverage or pH. Both Cd K-edge EXAFS and DFT results indicate the formation of double corner-sharing complexes on layer edge sites and mainly triple cornering-sharing complexes on vacancies. The distortion of both complexes results in the negative isotope fractionation onto the solids, and the slightly longer first Cd-O distances and a smaller number of nearest Mn atoms around Cd at edge sites probably account for the larger fractionation magnitude compared to that of vacancies. These results provide deep insights into Cd isotope fractionation mechanisms during interactions with phyllomanganates.

13.
World J Gastrointest Surg ; 16(6): 1582-1591, 2024 Jun 27.
Artigo em Inglês | MEDLINE | ID: mdl-38983354

RESUMO

BACKGROUND: Intraoperative persistent hypotension (IPH) during pancreaticoduodenectomy (PD) is linked to adverse postoperative outcomes, yet its risk factors remain unclear. AIM: To clarify the risk factors associated with IPH during PD, ensuring patient safety in the perioperative period. METHODS: A retrospective analysis of patient records from January 2018 to December 2022 at the First Affiliated Hospital of Nanjing Medical University identified factors associated with IPH in PD. These factors included age, gender, body mass index, American Society of Anesthesiologists classification, comorbidities, medication history, operation duration, fluid balance, blood loss, urine output, and blood gas parameters. IPH was defined as sustained mean arterial pressure < 65 mmHg, requiring prolonged deoxyepinephrine infusion for > 30 min despite additional deoxyepinephrine and fluid treatments. RESULTS: Among 1596 PD patients, 661 (41.42%) experienced IPH. Multivariate logistic regression identified key risk factors: increased age [odds ratio (OR): 1.20 per decade, 95% confidence interval (CI): 1.08-1.33] (P < 0.001), longer surgery duration (OR: 1.15 per additional hour, 95%CI: 1.05-1.26) (P < 0.01), and greater blood loss (OR: 1.18 per 250-mL increment, 95%CI: 1.06-1.32) (P < 0.01). A novel finding was the association of arterial blood Ca2+ < 1.05 mmol/L with IPH (OR: 2.03, 95%CI: 1.65-2.50) (P < 0.001). CONCLUSION: IPH during PD is independently associated with older age, prolonged surgery, increased blood loss, and lower plasma Ca2+.

14.
J Am Chem Soc ; 146(29): 20414-20424, 2024 Jul 24.
Artigo em Inglês | MEDLINE | ID: mdl-38982611

RESUMO

The structural dynamics of artificial assemblies, in aspects such as molecular recognition and structural transformation, provide us with a blueprint to achieve bioinspired applications. Here, we describe the assembly of redox-switchable chiral metal-organic cages Λ8/Δ8-[Pd6(CoIIL3)8]28+ and Λ8/Δ8-[Pd6(CoIIIL3)8]36+. These isomeric cages demonstrate an on-off chirality logic gate controlled by their chemical and stereostructural dynamics tunable through redox transitions between the labile CoII-state and static CoIII-state with a distinct Cotton effect. The transition between different states is enabled by a reversible redox process and chiral recognition originating in the tris-chelate Co-centers. All cages in two states are thoroughly characterized by NMR, ESI-MS, CV, CD, and X-ray crystallographic analysis, which clarify their redox-switching behaviors upon chemical reduction/oxidation. The stereochemical lability of the CoII-center endows the Λ8/Δ8-CoII-cages with efficient chiral-induction by enantiomeric guests, leading to enantiomeric isomerization to switch between Λ8/Δ8-CoII-cages, which can be stabilized by oxidation to their chemically inert forms of Λ8/Δ8-CoIII-cages. Kinetic studies reveal that the isomerization rate of the Δ8-CoIII-cage is at least an order of magnitude slower than that of the Δ8-CoII-cage even at an elevated temperature, while its activation energy is 16 kcal mol-1 higher than that of the CoII-cage.

15.
BMC Public Health ; 24(1): 2014, 2024 Jul 28.
Artigo em Inglês | MEDLINE | ID: mdl-39069625

RESUMO

INTRODUCTION: COVID-19 has demonstrated the importance of competent staff with expertise in public health emergency preparedness and response in the civil aviation system. The civil aviation system is a critical sentinel and checkpoint to prevent imported cases and slow the spread of communicable diseases. Understanding the current competencies of staff to deal with public health emergencies will help government agencies develop targeted training and evidence-based policies to improve their public health preparedness and response capabilities. METHODS: This cross-sectional pilot study was conducted from November 2022 to October 2023, involving 118 staff members from various positions within China's civil aviation system. A 59-item questionnaire was translated and developed according to a competency profile. Data were collected using the self-report questionnaire to measure the workforce's self-perceptions of knowledge and skills associated with public health emergency proficiency, categorized into (1) general competency, (2) preparedness competency, (3) response competency, and (4) recovery competency. KMO & Bartlett test and Cronbach's α reliability analysis were used to test the reliability and validity of the questionnaire. Descriptive statistics, independent sample T-test, ANOVA, and linear regression models were performed to analyze the competencies. RESULTS: A total of 107 staff members from the aviation system were surveyed in this study. The KMO & Bartlett test, (KMO = 0.919, P < 0.001) and Cronbach's α coefficients (α = 0.985) for this questionnaire were acceptable. The results suggested that respondents scored a mean of 6.48 out of 9 for the single question. However, the staff needed to acquire more knowledge in investigating epidemic information (5.92) and case managing (5.91) in the response stage. Overall, males scored higher (409.05 ± 81.39) than females (367.99 ± 84.97), with scores in the medical department (445.67 ± 72.01) higher than management (387.00 ± 70.87) and general department (362.32 ± 86.93). Additionally, those with completely subjective evaluation (425.79 ± 88.10) scored higher than the general group (374.39 ± 79.91). To predict the total score, female medical workers were more likely to have lower scores (ß = -34.5, P = 0.041). Compared with those in the medical department, the management workers (ß = -65.54, P = 0.008) and general workers (ß = -78.06, P < 0.001) were associated with a lower total score. CONCLUSIONS: There was still a gap between the public health emergency competencies of the civil aviation system and the demand. Staff in China's civil aviation systems demonstrated overall competence in public health emergency preparedness and response. However, there was a need to enhance the accumulation of practical experience. Implementing effective training programs for public health emergencies was recommended to mitigate knowledge gaps. Meanwhile, regular training evaluations were also recommended to give comprehensive feedback on the value of the training programs.


Assuntos
COVID-19 , Autorrelato , Humanos , Projetos Piloto , China , Estudos Transversais , Masculino , Feminino , Adulto , COVID-19/epidemiologia , COVID-19/prevenção & controle , Competência Profissional/normas , Saúde Pública , Aviação/normas , Pessoa de Meia-Idade , Inquéritos e Questionários , Defesa Civil/normas , Reprodutibilidade dos Testes
16.
J Am Chem Soc ; 146(31): 21677-21688, 2024 Aug 07.
Artigo em Inglês | MEDLINE | ID: mdl-39042557

RESUMO

Achieving high guest loading and multiguest-binding capacity holds crucial significance for advancement in separation, catalysis, and drug delivery with synthetic receptors; however, it remains a challenging bottleneck in characterization of high-stoichiometry guest-binding events. Herein, we describe a large-sized coordination cage (MOC-70-Zn8Pd6) possessing 12 peripheral pockets capable of accommodating multiple guests and a high-resolution electrospray ionization mass spectrometry (HR-ESI-MS)-based method to understand the solution host-guest chemistry. A diverse range of bulky guests, varying from drug molecules to rigid fullerenes as well as flexible host molecules of crown ethers and calixarenes, could be loaded into open pockets with high capacities. Notably, these hollow cage pockets provide multisites to capture different guests, showing heteroguest coloading behavior to capture binary, ternary, or even quaternary guests. Moreover, a pair of commercially applied drugs for the combination therapy of chronic lymphocytic leukemia (CLL) has been tested, highlighting its potential in multidrug delivery for combined treatment.


Assuntos
Espectrometria de Massas por Ionização por Electrospray , Éteres de Coroa/química , Calixarenos/química , Paládio/química , Zinco/química , Fulerenos/química , Estrutura Molecular
17.
J Environ Manage ; 363: 121318, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38852414

RESUMO

The urban integrated energy system (UIES) is the fundamental infrastructure supporting the operation of resilient cities. The resilience of UIES plays a critical role in effectively responding to extreme events. We provide a comprehensive review on the management of resilient UIES. Firstly, we examine the existing studies on the resilience of UIES through quantitative and qualitative methodologies. Secondly, it points out that the coupling characteristics of UIES have a dual impact on resilience. The definition of UIES resilience can be understood from three perspectives, namely partial resilience versus total resilience, physical resilience versus digital resilience, and current resilience versus future resilience. Thirdly, this review summarizes the strategies for improving the resilience of UIES across three distinct stages, namely before, during, and after extreme events. The resilience of UIES can be enhanced by effective measures to prediction, adaptation, and assessment. Finally, the challenges faced by management of resilient UIES are presented and discussed, in terms of mitigating compound risks, modeling complex systems, addressing data collection and quality issue, and collaborating within multi stakeholders.


Assuntos
Cidades
18.
Chemosphere ; 362: 142683, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38908451

RESUMO

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) are involuntary by-products of incomplete combustion and are highly toxic to humans and the environment. The Malaysian peat is often acidic or extremely acidic having high levels of chlorine and/or other organic acids that act as catalysts or precursors in PCDD/Fs formation. This study aims to predict PCDD/Fs emissions in peat soil using an artificial neural network (ANN) approach based on limited emission data and selected physico-chemical properties. The ANN's prediction performance is affected by uncertainties in its initial connection weights. To improve prediction performance, an optimisation algorithm, termed differential evolution (DE), is used to optimise the ANN's initial connection weights and bias. The study adopts several ANNs with fixed architecture to predict PCDD/Fs emissions, each consisting of a multilayer perceptron (MLP) with a backpropagation algorithm. Eight input variables and one output variable were adopted to train and test various neural network architectures using real-world datasets. The model optimisation procedure was conducted to ascertain the network architecture with the best predictive accuracy. The evolved ANN based on 5 hidden neurons, with the assistance of self-adaptive ensemble-based differential evolution with enhanced population sizing (SAEDE-EP), successfully produced the lowest MSEtest (6.1790 × 10-3) and highest R2 (0.97447) based on the mean among the other HNs. An evolutionary-optimised ANN-based methodology is a viable solution to predict PCDD/Fs in peat soil. It is cost-effective for pollution control, environmental monitoring and capable of aiding authorities prevent PCDD/Fs exposure, e.g., during a fire.


Assuntos
Dibenzofuranos Policlorados , Redes Neurais de Computação , Dibenzodioxinas Policloradas , Poluentes do Solo , Solo , Dibenzodioxinas Policloradas/análise , Dibenzofuranos Policlorados/análise , Solo/química , Poluentes do Solo/análise , Algoritmos , Monitoramento Ambiental/métodos , Malásia , Benzofuranos/análise
19.
Spectrochim Acta A Mol Biomol Spectrosc ; 317: 124459, 2024 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-38749202

RESUMO

A macrocyclic compound, hemicucurbit[6]uril (HemiQ[6]), is employed as the carbon source to produce a novel sort of carbon quantum dots (CQDs) with blue fluorescence in aqueous solution. The CQDs are fully identified by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Nuclear Magnetic Resonance (NMR), zeta potential, ultraviolet/visible (UV-vis) and photoluminescence spectroscopy (PL). The nanomaterial is developed for the analysis of Pb2+ in the light of the Resonance Rayleigh scattering (RRS) changes with the increasing Pb2+ concentration. The proposed probe emerges a high selectivity to Pb2+ and excellent sensitivity in the linear concentration range of 0-6 µM with a detection limit low to 0.42 µM, which is superior to the previous values of Pb2+ sensors, as well as the good anti-interference ability is confirmed by the specifical response to Pb2+ in the presence of other metal cations. Therefore, the proposed analysis of Pb2+ is explored for the application in real samples of tap water and lake water, in satisfied results of acceptable recoveries.

20.
Drug Saf ; 47(8): 759-769, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38720114

RESUMO

INTRODUCTION: The use of dipeptidyl peptidase-4 (DPP-4) inhibitors may be associated with an increased risk of gallbladder and bile duct disease among patients with type 2 diabetes. METHODS: We conducted a population-based cohort study using an active comparator, new-user design. We used data from the United Kingdom Clinical Practice Research Datalink to identify patients newly treated with either a DPP-4 inhibitor or sodium-glucose cotransporter-2 (SGLT-2) inhibitor between January 2013 and December 2020. We fitted Cox proportional hazards models with propensity score fine stratification weighting to estimate the hazard ratio (HR) and its 95% confidence interval (CI) for incident gallbladder and bile duct disease associated with DPP-4 inhibitors compared to SGLT-2 inhibitors. RESULTS: DPP-4 inhibitors were associated with a 46% increased risk of gallbladder and bile duct disease (4.3 vs. 3.0 events per 1000 person-years, HR 1.46, 95% CI 1.17-1.83). At 6 months and 1 year, 745 and 948 patients, respectively, would need to be treated with DPP-4 inhibitors for one patient to experience a gallbladder or bile duct disease. CONCLUSIONS: In this population-based cohort study, the use of DPP-4 inhibitors, when compared with SGLT-2 inhibitors, was associated with a moderately increased risk of gallbladder and bile duct disease among patients with type 2 diabetes. This outcome was still quite rare with a high number needed to harm at 6 months and 1 year.


Assuntos
Doenças dos Ductos Biliares , Diabetes Mellitus Tipo 2 , Inibidores da Dipeptidil Peptidase IV , Doenças da Vesícula Biliar , Humanos , Diabetes Mellitus Tipo 2/tratamento farmacológico , Inibidores da Dipeptidil Peptidase IV/efeitos adversos , Inibidores da Dipeptidil Peptidase IV/uso terapêutico , Masculino , Feminino , Pessoa de Meia-Idade , Estudos de Coortes , Idoso , Doenças da Vesícula Biliar/induzido quimicamente , Doenças da Vesícula Biliar/epidemiologia , Doenças dos Ductos Biliares/induzido quimicamente , Doenças dos Ductos Biliares/epidemiologia , Reino Unido/epidemiologia , Inibidores do Transportador 2 de Sódio-Glicose/efeitos adversos , Inibidores do Transportador 2 de Sódio-Glicose/uso terapêutico , Fatores de Risco , Modelos de Riscos Proporcionais , Hipoglicemiantes/efeitos adversos , Hipoglicemiantes/uso terapêutico , Adulto
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