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1.
Nano Lett ; 2024 Oct 23.
Artigo em Inglês | MEDLINE | ID: mdl-39441119

RESUMO

It is widely acknowledged that quantum entities with minimal mass cannot undergo spontaneous symmetry breaking due to strong quantum fluctuations. Here, we report the discovery of a positionally settled single electric dipole that can be manipulated and electrically polarized in a monolayer CoCl2-graphite heterostructure, which demonstrates an unprecedented example of spontaneous lattice-translational-symmetry breaking. Scanning tunneling microscopy and atomic force microscopy show that the solitons are intrinsic paraelectric dipoles driven by synchronous charge-lattice distortion around individual CoCl6 octahedrons. Both the dipole moment and lateral position of the soliton can be manipulated by the electric field exerted from the tip, which offers polarity-switchable and layout-designable electrostatic potential landscapes that determine the band bending configuration. This study exemplifies a brand-new type of local charge-lattice order, appealing for further research on the mechanism underlying the soliton robustness, and the electrically and positionally controllable single dipole supports the feasibility of band tailoring in device applications.

2.
BMC Med ; 21(1): 173, 2023 05 05.
Artigo em Inglês | MEDLINE | ID: mdl-37147645

RESUMO

BACKGROUND: Apatinib, a highly selective VEGFR2 inhibitor, significantly improved efficacy versus placebo as a third- and later-line treatment for advanced gastric cancer in phase 2 and 3 trials. This prospective, single-arm, multicenter phase IV AHEAD study was conducted to verify the safety and efficacy of apatinib in patients with advanced or metastatic gastric or gastroesophageal adenocarcinoma after at least two lines of systematic therapy in clinical practice settings. METHODS: Patients with advanced gastric cancer who had previously failed at least two lines of chemotherapy received oral apatinib until disease progression, death or unacceptable toxicity. The primary endpoint was safety. The secondary endpoints included objective response rate (ORR), disease control rate (DCR), progression-free survival (PFS) and overall survival (OS). Adverse events were summarized by the incidence rate. Median OS and PFS were estimated using the Kaplan-Meier method. ORR, DCR, OS at 3 and 6 months, and PFS at 3 and 6 months were calculated, and their 95% CIs were estimated according to the Clopper-Pearson method. RESULTS: Between May 2015 and November 2019, a total of 2004 patients were enrolled, and 1999 patients who received at least one dose of apatinib were assessed for safety. In the safety population, 87.9% of patients experienced treatment-related adverse events (TRAEs), with the most common hypertension (45.2%), proteinuria (26.5%), and white blood cell count decreased (25.3%). Additionally, 51% of patients experienced grade ≥ 3 TRAEs. Fatal TRAEs occurred in 57 (2.9%) patients. No new safety concerns were reported. Among the 2004 patients included in the intention-to-treat population, the ORR was 4.4% (95% CI, 3.6-5.4%), and DCR was 35.8% (95% CI, 33.7-38.0%). The median PFS was 2.7 months (95% CI 2.2-2.8), and the median OS was 5.8 months (95% CI 5.4-6.1). CONCLUSIONS: The findings in the AHEAD study confirmed the acceptable and manageable safety profile and clinical benefit of apatinib in patients with advanced gastric cancer as a third- or later-line of treatment. TRIAL REGISTRATION: This study was registered with ClinicalTrials.gov NCT02426034. Registration date was April 24, 2015.


Assuntos
Adenocarcinoma , Antineoplásicos , Neoplasias Gástricas , Humanos , Antineoplásicos/efeitos adversos , Neoplasias Gástricas/tratamento farmacológico , Estudos Prospectivos , Adenocarcinoma/tratamento farmacológico , Adenocarcinoma/patologia , Junção Esofagogástrica/patologia
3.
MAGMA ; 36(4): 651-658, 2023 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-36449124

RESUMO

BACKGROUND: This study aims to present a radiomic application in diagnosing the long head of biceps (LHB) tendinitis. Moreover, we evaluated whether machine learning-derived radiomic features recognize LHB tendinitis. PATIENTS AND METHODS: A total of 170 patients were reviewed. All LHB tendinitis patients were diagnosed under arthroscopy. Radiomic features were extracted from preoperative magnetic resonance imaging (MRI), and the input dataset was divided into a training set and a test set. For feature selection, the t test and least absolute shrinkage and selection operator (LASSO) methods were used, and random forest (RF) and support vector machine (SVM) were used as machine learning classifiers. The sensitivity, specificity, accuracy, and area under the curve (AUC) of each model's receiver operating characteristic (ROC) curves were calculated to evaluate model performance. RESULTS: In total, 851 radiomic features were extracted, with 109 radiomic features extracted using a t test and 20 radiomic features extracted using the LASSO method. The random forest classifier shows the highest sensitivity, specificity, accuracy, and AUC (0.52, 0.92, 0.73, and 0.72). CONCLUSION: The classifier contract by 20 radiomic features demonstrated a good ability to predict extra-articular LHB tendinitis.However because of poor segmentation reliability, the value of Radiomic in LHB tendinitis still needs to be further explored.


Assuntos
Imageamento por Ressonância Magnética , Humanos , Reprodutibilidade dos Testes , Estudos Retrospectivos , Imageamento por Ressonância Magnética/métodos , Curva ROC
4.
Proc Natl Acad Sci U S A ; 117(13): 7090-7094, 2020 Mar 31.
Artigo em Inglês | MEDLINE | ID: mdl-32179681

RESUMO

Electronic phase separation in complex oxides is the inhomogeneous spatial distribution of electronic phases, involving length scales much larger than those of structural defects or nonuniform distribution of chemical dopants. While experimental efforts focused on phase separation and established its correlation with nonlinear responses under external stimuli, it remains controversial whether phase separation requires quenched disorder for its realization. Early theory predicted that if perfectly "clean" samples could be grown, both phase separation and nonlinearities would be replaced by a bicritical-like phase diagram. Here, using a layer-by-layer superlattice growth technique we fabricate a fully chemically ordered "tricolor" manganite superlattice, and compare its properties with those of isovalent alloyed manganite films. Remarkably, the fully ordered manganite does not exhibit phase separation, while its presence is pronounced in the alloy. This suggests that chemical-doping-induced disorder is crucial to stabilize the potentially useful nonlinear responses of manganites, as theory predicted.

5.
Medicina (Kaunas) ; 59(2)2023 Feb 17.
Artigo em Inglês | MEDLINE | ID: mdl-36837591

RESUMO

Background and Objectives: Tunnel enlargement (TE) is a widely reported phenomenon after anterior cruciate ligament reconstruction (ACLR). Given the paucity of knowledge in the literature, it remains unclear whether screw position in the tunnel affects TE. This retrospective cohort study evaluated differences in postoperative tunnel enlargement rates (TER) and clinical results between anterior and posterior tibial interference screw insertion during single-bundle ACLR using autologous hamstring grafts. Materials and Methods: A group of consecutive patients that underwent primary arthroscopic single-bundle ACLR in our hospital were screened and divided into two groups based on the position of the tibial interference screw (determined by Computer Tomography within 3 days after surgery): anterior screw position group (A) and posterior screw position group (B). The bone tunnel size was measured using magnetic resonance imaging (MRI) performed 1 year after surgery. International Knee Documentation Committee (IKDC) score and the Knee Injury and Osteoarthritis Outcome Score (KOOS) were used for clinical results 1 year postoperatively. Results: 87 patients were included. The TER of Group A is higher than that of Group B (43.17% vs. 33.80%, p = 0.024). Group A showed a significant increase (12.1%) in enlargement rates at the joint line level than group B (43.77% vs. 31.67%, p = 0.004). Moreover, KOOS and IKDC scores improved in both groups. There were no significant differences in clinical outcomes between the two groups. Conclusions: One year after ACLR, patients with posterior screw showed significantly lower TE than patients with anterior screw. However, the position of screw did not lead to differences in clinical results over our follow-up period. Posterior screw position in the tibial tunnel maybe a better choice in terms of reducing TE. Whether the different screw positions affect the long-term TE and long-term clinical outcomes needs to be confirmed by further studies.


Assuntos
Lesões do Ligamento Cruzado Anterior , Reconstrução do Ligamento Cruzado Anterior , Humanos , Estudos Retrospectivos , Ligamento Cruzado Anterior , Articulação do Joelho/cirurgia , Tíbia/cirurgia , Parafusos Ósseos , Reconstrução do Ligamento Cruzado Anterior/métodos , Lesões do Ligamento Cruzado Anterior/cirurgia , Fêmur
6.
Proc Natl Acad Sci U S A ; 116(10): 4141-4146, 2019 Mar 05.
Artigo em Inglês | MEDLINE | ID: mdl-30787195

RESUMO

Characterization of the onset of a phase transition is often challenging due to the fluctuations of the correlation length scales of the order parameters. This is especially true for second-order structural-phase transition due to minute changes involved in the relevant lattice constants. A classic example is the cubic-to-tetragonal second-order phase transition in SrTiO3 (STO), which is so subtle that it is still unresolved. Here, we demonstrate an approach to resolve this issue by epitaxially grown rhombohedral La0.7Sr0.3MnO3 (LSMO) thin films on the cubic STO (100) substrate. The shear strain induced nanotwinning waves in the LSMO film are extremely sensitive to the cubic-to-tetragonal structural-phase transitions of the STO substrate. Upon cooling from room temperature, the development of the nanotwinning waves is spatially inhomogeneous. Untwinned, atomically flat domains, ranging in size from 100 to 300 nm, start to appear randomly in the twinned phase between 265 and 175 K. At ∼139 K, the untwinned, atomically flat domains start to grow rapidly into micrometer scale and finally become dominant at ∼108 K. These results indicate that the low-temperature tetragonal precursor phase of STO has already nucleated at 265 K, significantly higher than the critical temperature of STO (∼105 K). Our work paves a pathway to visualize the onset stages of structural-phase transitions that are too subtle to be observed using direct-imaging methods.

7.
Sensors (Basel) ; 22(22)2022 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-36433414

RESUMO

Density peak clustering is the latest classic density-based clustering algorithm, which can directly find the cluster center without iteration. The algorithm needs to determine a unique parameter, so the selection of parameters is particularly important. However, for multi-density data, when one parameter cannot satisfy all data, clustering often cannot achieve good results. Moreover, the subjective selection of cluster centers through decision diagrams is often not very convincing, and there are also certain errors. In view of the above problems, in order to achieve better clustering of multi-density data, this paper improves the density peak clustering algorithm. Aiming at the selection of parameter dc, the K-nearest neighbor idea is used to sort the neighbor distance of each data, draw a line graph of the K-nearest neighbor distance, and find the global bifurcation point to divide the data with different densities. Aiming at the selection of cluster centers, the local density and distance of each data point in each data division is found, a γ map is drawn, the average value of the γ height difference is calculated, and through two screenings the largest discontinuity point is found to automatically determine the cluster center and the number of cluster centers. The divided datasets are clustered by the DPC algorithm, and then the clustering results are perfected and integrated by using the cluster fusion rules. Finally, a variety of experiments are designed from various perspectives on various artificial simulated datasets and UCI real datasets, which demonstrate the superiority of the F-DPC algorithm in terms of clustering effect, clustering quality, and number of samples.


Assuntos
Algoritmos , Análise por Conglomerados
8.
Calcif Tissue Int ; 109(6): 675-684, 2021 12.
Artigo em Inglês | MEDLINE | ID: mdl-34259888

RESUMO

Observational studies suggest a link between depression and osteoporosis, but these may be subject to confounding and reverse causality. In this two-sample Mendelian randomization analysis, we included the large meta-analysis of genome-wide association studies for depression among 807,553 individuals (246,363 cases and 561,190 controls) of European descent, the large meta-analysis to identify genetic variants associated with femoral neck bone mineral density (FN-BMD), forearm BMD (FA-BMD) and lumbar spine BMD (LS-BMD) among 53,236 individuals of European ancestry, and the GWAS summary data of heel BMD (HE-BMD) and fracture among 426,824 individuals of European ancestry. The results revealed that genetic predisposition towards depression showed no causal effect on FA-BMD (beta-estimate: 0.091, 95% confidence interval [CI] - 0.088 to 0.269, SE:0.091, P value = 0.320), FN-BMD (beta-estimate: 0.066, 95% CI - 0.016 to 0.148, SE:0.042, P value = 0.113), LS-BMD (beta-estimate: 0.074, 95% CI - 0.029 to 0.177, SE:0.052, P value = 0.159), HE-BMD (beta-estimate: 0.009, 95% CI - 0.043 to 0.061, SE:0.027, P value = 0.727), or fracture (beta-estimate: 0.008, 95% CI - 0.071 to 0.087, SE:0.041, P value = 0.844). These results were also confirmed by multiple sensitivity analyses. Contrary to the findings of observational studies, our results do not reveal a causal role of depression in osteoporosis or fracture.


Assuntos
Análise da Randomização Mendeliana , Osteoporose , Densidade Óssea/genética , Depressão , Estudo de Associação Genômica Ampla , Humanos , Osteoporose/epidemiologia , Osteoporose/genética , Polimorfismo de Nucleotídeo Único
9.
Knee Surg Sports Traumatol Arthrosc ; 29(8): 2709-2716, 2021 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-33834257

RESUMO

PURPOSE: To determine the differences in anatomic parameters between ipsilateral dislocated knees and contralateral non-dislocated knees in patients with unilateral patellar dislocation and to identify any variations in ipsilateral knees contributing to contralateral anatomic abnormalities. METHODS: A total of 82 patients with unilateral patellar dislocation from 2016 to 2019 were retrospectively evaluated. Bilateral anatomic factors, including the tibial tubercle to trochlear groove (TT-TG) distance, lower limb rotational deformities, trochlear dysplasia, patella tilt, and patellar height, were assessed by CT. RESULTS: The study included 46 patients (32 females and 14 males, mean age ± SD 20.5 ± 6.8). The interobserver reliability of each parameter showed excellent agreement. The ipsilateral TT-TG distance (P = 0.004), patella tilt (P = 0.001), and patellar height (P = 0.01) were greater in the ipsilateral knees than in the contralateral knees. The lateral trochlea inclination (LTI) in the contralateral knees was larger than that in the ipsilateral knees (P = 0.022). There was a significant difference in the distribution of trochlear dysplasia of Dejour between the ipsilateral knees (dislocated side) and the contralateral knees (P = 0.036). However, bilateral femoral and/or tibial torsion, and bilateral knee joint rotation did not differ significantly. Binary logistic regression showed that only ipsilateral LTI revealed significant ORs of 8.83 (P = 0.016) and 7.64 (P = 0.018) with regard to contralateral abnormal tibial torsion and LTI, respectively. CONCLUSION: In patients with unilateral patellar dislocation, the ipsilateral TT-TG distance, patella tilt, and patellar height values were larger in the ipsilateral knees than in the contralateral knees, and trochlear dysplasia was more severe in the ipsilateral joints. The risks of contralateral pathological tibial torsion and LTI were 8.8- and 7.6-fold higher, respectively, in patients with abnormal ipsilateral LTI. LEVEL OF EVIDENCE: Level IV.


Assuntos
Instabilidade Articular , Luxação Patelar , Articulação Patelofemoral , Feminino , Humanos , Instabilidade Articular/diagnóstico por imagem , Articulação do Joelho/diagnóstico por imagem , Masculino , Patela/diagnóstico por imagem , Luxação Patelar/diagnóstico por imagem , Articulação Patelofemoral/diagnóstico por imagem , Reprodutibilidade dos Testes , Estudos Retrospectivos , Tíbia/diagnóstico por imagem
10.
BMC Pediatr ; 20(1): 87, 2020 02 24.
Artigo em Inglês | MEDLINE | ID: mdl-32093619

RESUMO

BACKGROUND: Low cardiac output syndrome (LCOS) is an important complication of cardiac surgery. It is associated with increased morbidity and mortality. The incidence of LCOS after surgery is high in patients with congenital heart disease (CHD). Therefore, determining the risk factors of LCOS has clinical significance for the management of CHD. This study aimed to analyze the risk factors of LCOS. METHODS: We conducted a retrospective analysis of children with CHD who underwent cardiac surgery at Shanghai Children's Medical Center between January 1, 2014, and December 31, 2017. Demographic characteristics and baseline data were extracted from the health data resource center of the hospital, which integrates clinical routine data including medical records, diagnoses, orders, surgeries, laboratory tests, imaging, nursing, and other subsystems. Logistic regressions were performed to analyze the risk factors of LCOS. RESULTS: Overall, 8660 infants with CHD were included, and 864 (9.98%) had LCOS after surgery. The multivariate regression analysis identified that age (OR 0.992, 95% CI: 0.988-0.997, p = 0.001), tricuspid regurgitation (1.192, 1.072-1.326, p = 0.001), Risk Adjustment in Congenital Heart Surgery-1 risk grade (1.166, 1.011-1.345, p = 0.035), aortic shunt (left-to-right: 1.37, 1.005-1.867, p = 0.046; bi-directional: 1.716, 1.138-2.587, p = 0.01), atrial shunt (left-to-right: 1.407, 1.097-1.805, p = 0.007; right-to-left: 3.168, 1.944-5.163, p < 0.001; bi-directional: 1.87, 1.389-2.519, p < 0.001), ventricular level shunt (left-to-right: 0.676, 0.486-0.94, p = 0.02; bi-directional: 2.09, 1.611-2.712, p < 0.001), residual shunt (3.489, 1.502-8.105, p = 0.004), left ventricular outflow tract obstruction (3.934, 1.673-9.254, p = 0.002), right ventricular outflow tract obstruction (3.638, 1.225-10.798, p = 0.02), circulating temperature (mild hypothermia: 1.526, 95% CI: 1.205-1.934, p < 0.001; middle and low temperature: 1.738, 1.236-2.443, p = 0.001), duration of cardiopulmonary bypass (1.009, 1.006-1.012, p < 0.001), myocardial preservation using histidine-tryptophan-ketoglutarate (1.677, 1.298-2.167, p < 0.001), and mitral insufficiency (1.714, 1.239-2.37, p < 0.001) were independent risk predictors of LCOS. CONCLUSIONS: The incidence of postoperative LCOS in CHD children remains high. Circulation temperature, myocardial preservation using histidine-tryptophan-ketoglutarate, and usage of residual shunt after surgery were independent risk predictors for LCOS.


Assuntos
Baixo Débito Cardíaco , Procedimentos Cirúrgicos Cardíacos , Cardiopatias Congênitas , Baixo Débito Cardíaco/diagnóstico , Baixo Débito Cardíaco/epidemiologia , Baixo Débito Cardíaco/etiologia , Procedimentos Cirúrgicos Cardíacos/efeitos adversos , Criança , Pré-Escolar , China , Feminino , Cardiopatias Congênitas/complicações , Cardiopatias Congênitas/cirurgia , Humanos , Lactente , Masculino , Complicações Pós-Operatórias/epidemiologia , Complicações Pós-Operatórias/etiologia , Estudos Retrospectivos , Fatores de Risco , Volume Sistólico , Função Ventricular Esquerda
11.
Proc Natl Acad Sci U S A ; 113(33): 9228-31, 2016 08 16.
Artigo em Inglês | MEDLINE | ID: mdl-27482108

RESUMO

In complex oxides systems such as manganites, electronic phase separation (EPS), a consequence of strong electronic correlations, dictates the exotic electrical and magnetic properties of these materials. A fundamental yet unresolved issue is how EPS responds to spatial confinement; will EPS just scale with size of an object, or will the one of the phases be pinned? Understanding this behavior is critical for future oxides electronics and spintronics because scaling down of the system is unavoidable for these applications. In this work, we use La0.325Pr0.3Ca0.375MnO3 (LPCMO) single crystalline disks to study the effect of spatial confinement on EPS. The EPS state featuring coexistence of ferromagnetic metallic and charge order insulating phases appears to be the low-temperature ground state in bulk, thin films, and large disks, a previously unidentified ground state (i.e., a single ferromagnetic phase state emerges in smaller disks). The critical size is between 500 nm and 800 nm, which is similar to the characteristic length scale of EPS in the LPCMO system. The ability to create a pure ferromagnetic phase in manganite nanodisks is highly desirable for spintronic applications.

12.
Phys Rev Lett ; 120(26): 267202, 2018 Jun 29.
Artigo em Inglês | MEDLINE | ID: mdl-30004745

RESUMO

At ultrafast timescales, the initial and final states of a first-order metal-insulator transition often coexist forming clusters of the two phases. Here, we report an unexpected third long-lived intermediate state emerging at the photoinduced first-order metal-insulator transition of La_{0.325}Pr_{0.3}Ca_{0.375}MnO_{3}, known to display submicrometer length-scale phase separation. Using magnetic force microscopy and time-dependent magneto-optical Kerr effect, we determined that the third state is a nanoscale mixture of the competing ferromagnetic metallic and charge-ordered insulating phases, with its own physical properties. This discovery bridges the two different families of colossal magnetoresistant manganites known experimentally and shows for the first time that the associated states predicted by theory can coexist in a single sample.

13.
Neurochem Res ; 43(12): 2446-2459, 2018 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-30382449

RESUMO

Perfluorooctanesulfonate (PFOS) may cause neurotoxicity through the initiation of oxidative stress. In the current study, we investigated the role of anti-oxidant nuclear factor erythroid 2-related factor 2 (Nrf2) pathway in PFOS-induced neurotoxicity. We found that human neuroblastoma SH-SY5Y cells exhibited significant apoptotic cell death following PFOS exposure, and this process was accompanied with apparent accumulation of reactive oxidative species (ROS). In addition, we revealed that PFOS exposure caused marked activation of Nrf2 pathway and the expression of Nrf2 transcription target heme oxygenase-1. We further found that pre-treatment with ROS scavenger N-acetyl-L-cysteine (NAC) dramatically ameliorated PFOS-induced ROS production and Nrf2 signaling. In keeping with these findings, western blot and Cell Counter Kit-8 analyses revealed that pre-incubation with NAC suppressed PFOS-induced expression of pro-apoptotic proteins and impairment of neuronal viability. Moreover, antagonizing Nrf2 pathway with Nrf2 inhibitor brusatol resulted in increased ROS production and enhanced PFOS-induced expression of apoptosis related proteins. Finally, we showed that PFOS exposure altered mitochondrial transmembrane potential and disrupted normal mitochondrial morphology in SH-SY5Y cells. Whereas treatment with NAC ameliorated PFOS-induced mitochondrial disorders, co-incubation with brusatol augmented PFOS-induced mitochondrial deficits, consequently contributing to neuronal apoptosis. These results manifest that Nrf2 pathway plays a protective role in PFOS-induced neurotoxicity, providing new insights into the prevention and treatment of PFOS-related toxicities.


Assuntos
Ácidos Alcanossulfônicos/toxicidade , Apoptose/fisiologia , Fluorocarbonos/toxicidade , Fator 2 Relacionado a NF-E2/metabolismo , Neuroproteção/fisiologia , Estresse Oxidativo/fisiologia , Transdução de Sinais/fisiologia , Apoptose/efeitos dos fármacos , Linhagem Celular Tumoral , Relação Dose-Resposta a Droga , Humanos , Neuroproteção/efeitos dos fármacos , Estresse Oxidativo/efeitos dos fármacos , Transdução de Sinais/efeitos dos fármacos
14.
Proc Natl Acad Sci U S A ; 112(31): 9558-62, 2015 Aug 04.
Artigo em Inglês | MEDLINE | ID: mdl-26195791

RESUMO

The interesting transport and magnetic properties in manganites depend sensitively on the nucleation and growth of electronic phase-separated domains. By fabricating antidot arrays in La0.325Pr0.3Ca0.375MnO3 (LPCMO) epitaxial thin films, we create ordered arrays of micrometer-sized ferromagnetic metallic (FMM) rings in the LPCMO films that lead to dramatically increased metal-insulator transition temperatures and reduced resistances. The FMM rings emerge from the edges of the antidots where the lattice symmetry is broken. Based on our Monte Carlo simulation, these FMM rings assist the nucleation and growth of FMM phase domains increasing the metal-insulator transition with decreasing temperature or increasing magnetic field. This study points to a way in which electronic phase separation in manganites can be artificially controlled without changing chemical composition or applying external field.

15.
Environ Sci Technol ; 50(11): 5857-63, 2016 06 07.
Artigo em Inglês | MEDLINE | ID: mdl-27128100

RESUMO

Cleavage of the strong carbon-fluorine bonds is critical for elimination of perfluorooctanoic acid (PFOA) from the environment. In this work, we investigated the decomposition of PFOA with the SiC/graphene catalyst under UV light irradiation. The decomposition rate constant (k) with SiC/graphene was 0.096 h(-1), 2.2 times higher than that with commercial nano-TiO2. Surface fluorination on SiC/graphene was analyzed by X-ray photoelectron spectroscopy (XPS), revealing the conversions of Si-H bonds into Si-F bonds. A different route was found to generate the reactive Si-H bonds on SiC/graphene, substituting for silylium (R3Si(+)) to activate C-F bonds. During the activation process, photogenerated electrons on SiC transfer rapidly to perfluoroalkyl groups by the medium of graphene, further reducing the electron cloud density of C-F bonds to promote the activation. The hydrogen-containing hydrodefluorination intermediates including (CF3(CF2)2CFH, CF3(CF2)3CH2, CF3(CF2)4CH2, and CF3(CF2)4CFHCOOH) were detected to verify the hydrodefluorination process. The photoinduced hydrodefluorination mechanisms of PFOA can be consequently inferred as follows: (1) fluorine atoms in perfluoroalkyl groups were replaced by hydrogen atoms due to the nucleophilic substitution reaction via the Si-H/C-F redistribution, and (2) generation of CH2 carbene from the hydrogen-containing perfluoroalkyl groups and the C-C bonds scission by the Photo-Kolbe decarboxylation reaction under UV light excitation. This photoinduced hydrodefluorination provides insight into the photocatalytic decomposition of perfluorocarboxylic acids (PFCAs) in an aqueous environment.


Assuntos
Grafite , Espectroscopia Fotoeletrônica , Catálise , Raios Ultravioleta , Purificação da Água
16.
Phys Chem Chem Phys ; 17(26): 17421-8, 2015 Jul 14.
Artigo em Inglês | MEDLINE | ID: mdl-26076905

RESUMO

Triclosan (TCS) is a potential threat to the environment and human health. Photocatalysis can be used to degrade TCS, but the photocatalytic efficiency is usually limited by the photoabsorptivity and photostability of the photocatalyst. In addition, some toxic by-products might also be generated during photocatalytic processes. In this study, we prepared Au-coated Cu2O nanowire arrays (Au-Cu2O NWAs) by beam sputtering Au onto Cu2O nanowires grown from a Cu foil. We found that photocatalytic degradation of TCS under visible light (420 nm < λ < 780 nm) irradiation and Au-Cu2O NWAs had several advantages. Au-Cu2O NWAs had good photoabsorptivity, high photostability (negligible activity loss after 16 runs), excellent photocatalytic activity (47.6 times faster than that of Cu2O), and low yield of dichlorodibenzo-dioxins/dichlorohydroxydibenzofurans. The degradation intermediates were identified as chlorophenoxyphenol, phenoxyphenol, chlorophenol, catechol, phenol, benzoquinone, and lower volatile acids. We developed the degradation pathway of TCS which follows electron reduction and then oxidation by reactive oxygen species. The mechanism was developed and strengthened using the radical trapping and other measurements. The unusual mechanism and photostability of Au-Cu2O NWAs were attributed to the Au/Cu2O/Cu "sandwich"-like structure. This structure yields a sustained and steady internal electric field, raises the conduction band of Cu2O, reinforces the reductive activity of the photo-generated electrons, and eliminates the photo-generated holes that are responsible for the photo-etching of Cu2O.


Assuntos
Cobre/química , Ouro/química , Luz , Nanofios/química , Processos Fotoquímicos , Triclosan/química , Triclosan/efeitos da radiação , Catálise , Oxirredução , Temperatura
17.
Chemosphere ; 352: 141333, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38336036

RESUMO

Persulfate-based advanced oxidation processes (PS-AOPs) show a bright prospect in sewage purification. The development of efficient catalysts with simple preparation process and eco-friendliness is the key for their applying in practical water treatment. Herein, a bimetallic Cu-Fe metal organic framework (MOF) was simply synthesized by using one-pot solvothermal methods and employed for activating peroxymonosulfate (PMS) to degrade organic pollutants in water. The Cu-Fe-MOF/PMS exhibited excellent degradation efficiencies (over 95% in 30 min) for a variety of pollutants, including phenol, bisphenol A, 2,4-dichlorophenol, methyl blue, rhodamine B, tetracycline and sulfamethoxazole. The degradation efficiency was impacted by dosages of Cu-Fe-MOF, PMS concentrations, reaction temperature, solution pH and anionic species. Phenol could be efficiently decomposed in a wide pH range of 5-9, with the highest degradation and mineralization efficiency of nearly 100% and 70%, respectively. Free radicals and non-free radicals participated in degrading of phenol at the same time, with dominantly free radical process, because sulfate radicals (SO4·-) and hydroxyl radicals (·OH) were the primary active substances by contribution calculation. Cu-Fe-MOF was acted as electron shuttle between molecules of phenol and PMS, and the cooperation effect of Fe and Cu on the Cu-Fe-MOF promoted the electron transfer, achieving the high degradation efficiency of phenol. Thus, Cu-Fe-MOF is an ideal catalyst for activating PMS, which is conducive to promote the applying of catalyst-activated PMS processes for practical wastewater treatments.


Assuntos
Poluentes Ambientais , Estruturas Metalorgânicas , Ferro/química , Poluentes Ambientais/química , Elétrons , Peróxidos/química , Fenóis
18.
Chemosphere ; 346: 140636, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-37949189

RESUMO

Micro/nanoplastics (MNPs) have been increasingly found in environments, food, and organisms, arousing wide public concerns. MNPs may enter food chains through water, posing a threat to human health. Therefore, efficient and environmentally friendly technologies are needed to remove MNPs from contaminated aqueous environments. Advanced oxidation processes (AOPs) produce a vast amount of active species, such as hydroxyl radicals (·OH), known for their strong oxidation capacity. As a result, an increasing number of researchers have focused on using AOPs to decompose and remove MNPs from water. This review summarizes the progress in researches on the removal of MNPs from water by AOPs, including ultraviolet photolysis, ozone oxidation, photocatalysis, Fenton oxidation, electrocatalysis, persulfate oxidation, and plasma oxidation, etc. The removal efficiencies of these AOPs for MNPs in water and the influencing factors are comprehensively analyzed, meanwhile, the oxidation mechanisms and reaction pathways are also discussed in detail. Most AOPs can achieve the degradation of MNPs, mainly manifest as the decrease of particle size and the increase of mass loss, but the mineralization rate is low, thus requiring further optimization for improved performance. Investigating various AOPs is crucial for achieving the complete decomposition of MNPs in water. AOPs will undoubtedly play a vital role in the future for the removal of MNPs from water.


Assuntos
Poluentes Químicos da Água , Purificação da Água , Humanos , Água , Microplásticos , Poluentes Químicos da Água/análise , Oxirredução
19.
Sci Total Environ ; 946: 174200, 2024 Oct 10.
Artigo em Inglês | MEDLINE | ID: mdl-38936705

RESUMO

Alternatives are being developed to replace fluorinated persistent organic pollutants (POPs) listed in the Stockholm Convention, bypass environmental regulations, and overcome environmental risks. However, the extensive usage of fluorinated POPs alternatives has revealed potential risks such as high exposure levels, long-range transport properties, and physiological toxicity. Therefore, it is imperative to rethink the alternatives and their treatment technologies. This review aims to consider the existing destructive technologies for completely eliminating fluorinated POPs alternatives from the earth based on the updated classification and risks overview. Herein, the types of common alternatives were renewed and categorized, and their risks to the environment and organisms were concluded. The efficiency, effectiveness, energy utilization, sustainability, and cost of various degradation technologies in the treatment of fluorinated POPs alternatives were reviewed and evaluated. Meanwhile, the reaction mechanisms of different fluorinated POPs alternatives are systematically generalized, and the correlation between the structure of alternatives and the degradation characteristics was discussed, providing mechanistic insights for their removal from the environment. Overall, the review supplies a theoretical foundation and reference for the control and treatment of fluorinated POPs alternatives pollution.

20.
Curr Res Food Sci ; 8: 100754, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38736909

RESUMO

Chronic stress disrupts the emotional and energetic balance, which may lead to abnormal behaviors such as binge eating. This overeating behavior alleviating the negative emotions is called emotional eating, which may exacerbate emotional instability and lead to obesity. It is a complex and multifaceted process that has not yet been fully understood. In this study, we constructed an animal model of chronic mild stress (CMS)-induced emotional eating. The emotional eating mice were treated with tryptophan for 21 days to reveal the key role of tryptophan. Furthermore, serum-targeted metabolomics, immunohistochemical staining, qPCR and ELISA were performed. The results showed that CMS led to the binge eating behavior, accompanied by the disturbed intestinal tryptophan-derived serotonin (5-hydroxytryptamine; 5-HT) metabolic pathways. Then we found that tryptophan supplementation improved depression and anxiety-like behaviors as well as abnormal eating behaviors. Tryptophan supplementation improved the abnormal expression of appetite regulators (e.g., AgRP, OX1R, MC4R), and tryptophan supplementation also increased the tryptophan hydroxylase 2 (tph2) and 5-HT receptors in the hypothalamus of CMS mice, which indicates that the 5-HT metabolic pathway influences feeding behavior. In vitro experiments confirmed that 5-HT supplementation ameliorated corticosterone-induced aberrant expression of appetite regulators, such as AgRP and OX1R, in the hypothalamic cell line. In conclusion, our findings revealed that the tryptophan-derived 5-HT pathway plays an important role in emotional eating, especially in providing targeted therapy for stress-induced obesity.

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