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1.
Small ; : e2402863, 2024 May 19.
Artigo em Inglês | MEDLINE | ID: mdl-38764314

RESUMO

Facing the increasing global shortage of freshwater resources, this study presents a suspended multilayer evaporator (SMLE), designed to tackle the principal issues plaguing current solar-driven interfacial evaporation technologies, specifically, substantial thermal losses and limited water production. This approach, through the implementation of a multilayer structural design, enables superior thermal regulation throughout the evaporation process. This evaporator consists of a radiation damping layer, a photothermal conversion layer, and a bottom layer that leverages radiation, wherein the bottom layer exhibits a notable infrared emissivity. The distinctive feature of the design effectively reduces radiative heat loss and facilitates dual-interface evaporation by heating the water surface through mid-infrared radiation. The refined design leads to a notable evaporation rate of 2.83 kg m-2 h-1. Numerical simulations and practical performance evaluations validate the effectiveness of the multilayer evaporator in actual use scenarios. This energy-recycling and dual-interface evaporation multilayered approach propels the design of high-efficiency solar-driven interfacial evaporators forward, presenting new insights into developing effective water-energy transformation systems.

2.
Small ; 20(2): e2305473, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-37688298

RESUMO

Traditional nonlinear optical (NLO) crystals are exclusively limited to ionic crystals with π-conjugated groups and it is a great challenge to achieve a subtle balance between second-harmonic generation, bandgap, and birefringence for them, especially in the deep-UV spectrum region (Eg  > 6.20 eV). Herein, a non-π-conjugated molecular crystal, NH3 BH3 , which realizes such balance with a large second-harmonic generation response (2.0 × KH2 PO4 at 1064 nm, and 0.45 × ß-BaB2 O4 at 532 nm), deep-UV transparency (Eg > 6.53 eV), and moderate birefringence (Δn = 0.056@550 nm) is reported. As a result, NH3 BH3 exhibits a large quality factor of 0.32, which is evidently larger than those of non-π-conjugated sulfate and phosphate ionic crystals. Using an unpolished NH3 BH3 crystal, effective second-harmonic generation outputs are observed at different wavelengths. These attributes indicate that NH3 BH3 is a promising candidate for deep-UV NLO applications. This work opens up a new door for developing high-performance deep-UV NLO crystals.

3.
Biol Reprod ; 110(5): 895-907, 2024 May 09.
Artigo em Inglês | MEDLINE | ID: mdl-38267362

RESUMO

It is known that the oocyte has a limited capacity to acquire and metabolize glucose, and it must rely on cumulus cells (CCs) to take up glucose and produce pyruvate for use to produce ATP through oxidative phosphorylation. We therefore propose that miRNAs might regulate glucose metabolism (GM) in CCs and might be used as markers for oocyte quality assessment. Here, mouse CC models with impaired glycolysis or pentose phosphate pathway (PPP) were established, and miRNAs targeting the key enzymes in glycolysis/PPP were predicted using the miRNA target prediction databases. Expression of the predicted miRNAs was compared between CCs with normal and impaired glycolysis/PPP to identify candidate miRNAs. Function of the candidate miRNAs was validated by transfecting CCs or cumulus-oocyte-complexes (COCs) with miRNA inhibitors and observing effects on glucose metabolites of CCs and on competence of oocytes. The results validated that miR-23b-3p, let-7b-5p, 34b-5p and 145a-5p inhibited glycolysis, and miR-24-3p, 3078-3p,183-5p and 7001-5p inhibited PPP of CCs. Our observation using a more physiologically relevant model (intact cultured COCs) further validated the four glycolysis-targeting miRNAs we identified. Furthermore, miR-let-7b-5p, 34b-5p and 145a-5p may also inhibit PPP, as they decreased the production of glucose-6-phosphate. In conclusion, miRNAs play critical roles in GM of CCs and may be used as markers for oocyte quality assessment. Summary sentence:  We identified and validated eight new miRNAs that inhibit glycolysis and/or pentose phosphate pathways in cumulus cells (CCs) suggesting that miRNAs play critical roles in glucose metabolism of CCs and may be used for oocyte quality markers.


Assuntos
Células do Cúmulo , Glucose , Glicólise , MicroRNAs , Animais , Células do Cúmulo/metabolismo , MicroRNAs/metabolismo , MicroRNAs/genética , Camundongos , Glucose/metabolismo , Feminino , Glicólise/fisiologia , Via de Pentose Fosfato , Oócitos/metabolismo
4.
J Exp Bot ; 75(5): 1314-1330, 2024 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-38069660

RESUMO

Sphingolipids are membrane lipids and play critical roles in signal transduction. Ceramides are central components of sphingolipid metabolism that are involved in cell death. However, the mechanism of ceramides regulating cell death in plants remains unclear. Here, we found that ceramides accumulated in mitochondria of accelerated cell death 5 mutant (acd5), and expression of mitochondrion-localized ceramide kinase (ACD5) suppressed mitochondrial ceramide accumulation and the acd5 cell death phenotype. Using immuno-electron microscopy, we observed hyperaccumulation of ceramides in acer acd5 double mutants, which are characterized by mutations in both ACER (alkaline ceramidase) and ACD5 genes. The results confirmed that plants with specific ceramide accumulation exhibited localization of ceramides to mitochondria, resulting in an increase in mitochondrial reactive oxygen species production. Interestingly, when compared with the wild type, autophagy-deficient mutants showed stronger resistance to ceramide-induced cell death. Lipid profiling analysis demonstrated that plants with ceramide accumulation exhibited a significant increase in phosphatidylethanolamine levels. Furthermore, exogenous ceramide treatment or endogenous ceramide accumulation induces autophagy. When exposed to exogenous ceramides, an increase in the level of the autophagy-specific ubiquitin-like protein, ATG8e, associated with mitochondria, where it directly bound to ceramides. Taken together, we propose that the accumulation of ceramides in mitochondria can induce cell death by regulating autophagy.


Assuntos
Proteínas de Arabidopsis , Arabidopsis , Ceramidas/metabolismo , Ceramidas/farmacologia , Arabidopsis/metabolismo , Mitocôndrias/metabolismo , Autofagia , Morte Celular , Fosfotransferases (Aceptor do Grupo Álcool)/genética , Proteínas de Arabidopsis/genética , Proteínas de Arabidopsis/metabolismo
5.
Inorg Chem ; 63(9): 4412-4418, 2024 Mar 04.
Artigo em Inglês | MEDLINE | ID: mdl-38381086

RESUMO

Due to the flexible structural tunability and excellent photoelectric performance, hybrid organic-inorganic metal halides (OIMHs) have attracted intensive attention and become a hot topic in the field of materials. It is important and necessary to explore new OIMHs and study their structure-property relationship. In this work, a new lead-free OIMH, (C5N2H14Cl)GeCl3, is synthesized by the combination of hydrothermal and solution methods. This compound features a zero-dimensional structure composed of inorganic [GeCl3]- trigonal pyramids surrounded by isolated Cl- anions and organic (C5N2H14)2+ cations. Preliminary characterization and first-principles calculations are performed to study its basic optical properties. Interestingly, (C5N2H14Cl)GeCl3 shows weak blue emission under ultraviolet excitation, and the intrinsic mechanism is discussed.

6.
Bioorg Chem ; 151: 107653, 2024 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-39024803

RESUMO

This comprehensive review undertakes a meticulous scrutiny of the synthesis and clinical applications pertaining to small-molecule tyrosine kinase inhibitors (TKIs) directed towards the human epidermal growth factor receptor 2 (HER2), a pivotal protagonist in the pathogenesis of cancer. Focused on compounds like lapatinib, neratinib, and tucatinib, the review delves into the intricate synthesis strategies, emphasizing the challenges associated with their structural complexity. The clinical utilization of HER2 TKIs underscores noteworthy strides in the therapeutic landscape for HER2-positive breast and gastric malignancies. Lapatinib, a dual HER2/ epidermal growth factor receptor (EGFR) inhibitor, has demonstrated efficacy in combination therapies, addressing the need for overcoming resistance mechanisms. Neratinib, an irreversible HER2 inhibitor, presents a promising avenue for patients with refractory tumors. Tucatinib, strategically engineered to traverse the blood-brain barrier, epitomizes a groundbreaking advancement in the management of metastatic HER2-positive breast cancer manifesting cerebral involvement. Despite their success, challenges such as resistance mechanisms and off-target effects persist, urging continuous research for the development of next-generation HER2 TKIs. This comprehensive review serves as a valuable resource for pharmaceutical scientists, offering insights into the synthetic intricacies and clinical impact of small-molecule TKIs targeting HER2.

7.
Clin Radiol ; 79(3): e453-e461, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38160104

RESUMO

AIM: To establish an artificial neural network (ANN) model to predict subsolid nodules (SSNs) before percutaneous core-needle biopsy (PCNB). The results of the two methods were compared to provide guidance on the treatment of SSNs. MATERIALS AND METHODS: This was a single-centre retrospective study using data from 1,459 SSNs between 2013 and 2021. The ANN was developed using data from patients who underwent surgery following computed tomography (CT) (SFC) and validated using data from patients who underwent surgery following biopsy (SFB). The prediction results of the ANN for the PCNB group and the histopathological results obtained after biopsy were compared with the histopathological results of lung nodules in the same group after surgery. Additionally, the choice of predictors for PCNB was analysed using multivariate analysis. RESULTS: There was no significant difference between the accuracies of the ANN and PCNB in the SFB group (p=0.086). The sensitivity of PCNB was lower than that of the ANN (p=0.000), but the specificity was higher (p=0.001). PCNB had better diagnostic ability than the ANN. The incidence of precursor lesions and non-neoplastic lesions in the SFB group was lower than that in the SFC group (p=0.000). A history of malignant tumours, size (2-3 cm), volume (>400 cm3) and mean CT value (≥-450 HU) are important factors for selecting PCNB. CONCLUSIONS: Both ANN and PCNB have comparable accuracy in diagnosing SSNs; however, PCNB has a slightly higher diagnostic ability than ANN. Selecting appropriate patients for PCNB is important for maximising the benefit to SSN patients.


Assuntos
Neoplasias Pulmonares , Nitrobenzenos , Tomografia Computadorizada por Raios X , Humanos , Estudos Retrospectivos , Biópsia , Biópsia com Agulha de Grande Calibre , Tomografia Computadorizada por Raios X/métodos , Neoplasias Pulmonares/diagnóstico por imagem , Neoplasias Pulmonares/patologia
8.
J Chem Phys ; 161(6)2024 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-39132791

RESUMO

Forte is an open-source library specialized in multireference electronic structure theories for molecular systems and the rapid prototyping of new methods. This paper gives an overview of the capabilities of Forte, its software architecture, and examples of applications enabled by the methods it implements.

9.
Biochem Genet ; 2024 Apr 29.
Artigo em Inglês | MEDLINE | ID: mdl-38684626

RESUMO

Hepatocellular carcinoma (HCC) is a significant cancer with limited treatments and a poor prognosis, with the basement membrane (BM) playing a crucial role in its initiation and growth. This study utilized data from The Cancer Genome Atlas and the Gene Expression Omnibus (GEO) databases to identify basement membrane-related genes differentially expressed in HCC. Through gene co-expression analysis, BM-associated long non-coding RNAs (lncRNAs) were discovered. LncRNAs related to HCC survival were selected via univariate analysis, and a prognostic model was constructed using LASSO regression and multivariate analysis. This model effectively classified HCC patients into high and low-risk groups, uncovering significant differences in prognosis, immune response, mutation, and drug sensitivity. Six BM-related lncRNAs (GSEC, MIR4435-2HG, AC092614.1, AC127521.1, LINC02580, and AC008050.1) were validated in normal and HCC cell lines, and the key role of AC092614.1 in regulating proliferation, migration, and invasion of HCC cells in vitro was explored. This research emphasizes the prognostic and therapeutic relevance of BM-related lncRNAs in HCC, highlighting AC092614.1's role in disease progression and as a potential target for targeted therapy.

10.
Molecules ; 29(15)2024 Jul 29.
Artigo em Inglês | MEDLINE | ID: mdl-39124983

RESUMO

In the present work, deep eutectic solvents (DESs) were synthesized in a one-step process by heating the hydrogen bond acceptors (HBAs) tetrabutylammonium bromide and tetrabutylphosphonium bromide, along with two hydrogen bond donors (HBDs) ethanolamine and N-methyldiethanolamine, which were mixed in certain molar ratios. This mixture was then mixed with water to form a DES + water system. The densities of the prepared DES + water systems were successfully measured using the U-tube oscillation method under atmospheric pressure over a temperature range of 293.15-363.15 K. The CO2 trapping capacity of the DES + water systems was investigated using the isovolumetric saturation technique at pressures ranging from 0.1 MPa to 1 MPa and temperatures ranging from 303.15 K to 323.15 K. A semi-empirical model was employed to fit the experimental CO2 solubility data, and the deviations between the experimental and fitted values were calculated. At a temperature of 303.15 K and a pressure of 100 kPa, the CO2 solubilities in the DES + water systems of TBAB and MEA, with molar ratios of 1:8, 1:9, and 1:10, were measured to be 0.1430 g/g, 0.1479 g/g, and 0.1540 g/g, respectively. Finally, it was concluded that the DES + water systems had a superior CO2 capture capacity compared to the 30% aqueous monoethanolamine solution commonly used in industry, indicating the potential of DES + water systems for CO2 capture.

11.
J Community Psychol ; 52(7): 799-816, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-38975871

RESUMO

As the smallest spatial unit in the city, the community should be an important space for healing the urban population. This paper presents a systematic review summarizing studies on community healing environments. The study identified 75 publications. The research findings are as follows: the main intervening variables include restorativeness, emotions and mood, stress, and well-being. Little attention has been paid to the intervening variables including social support, environmental preferences and satisfaction, place attachment, behavior types that respond to personal will, self-fulfillment, and the spirit of personal culture. The various types of natural environments in communities have been given focused attention for a long time. However, the superiority of the natural environment should not be a reason to underestimate the healing benefits of community spaces. The mechanisms by which environmental characteristics are transformed into positive individual influences through intervening variables should be explored.


Assuntos
Satisfação Pessoal , Humanos , Apoio Social , Características de Residência , Meio Ambiente , Meio Social , Emoções
12.
Small ; : e2307754, 2023 Dec 10.
Artigo em Inglês | MEDLINE | ID: mdl-38072773

RESUMO

In this work, a novel high entropy hydroxide NiCoMoMnZn-layered double hydroxide(LDH) is synthesized as an electrode material for supercapacitors using a novel template re-etching method to promote the energy density. As a positive electrode material for supercapacitors, NiCoMoMnZn-LDH has the advantage of a uniform distribution of elements, high specific surface area, porous and stable structure. More importantly, the specific capacitance can reach 1810.2 F g-1 at the current density of 0.5 A g-1 , and the NiCoMoMnZn-LDH//AC HSC assembled from the material has an energy density of up to 62.1 Wh kg-1 at a power density of 475 W kg-1 . Moreover, the influence of different compositions on their morphological, structural, and electrochemical properties is investigated based on the characterization results. Then, the synergistic mechanism among the components of the high entropy NiCoMoMnZn-LDH is revealed in detail by DFT calculations. In addition, the synthesis strategy proposed in this work for high-entropy hydroxides exhibits universality. Experimental results show that the proposed strategy successfully avoids not only phase separation and element aggregation in the formation of high entropy materials, but also reduces structural distortion, which is beneficial for efficient and large-scale synthesis of high entropy hydroxides.

13.
J Transl Med ; 21(1): 73, 2023 02 03.
Artigo em Inglês | MEDLINE | ID: mdl-36737759

RESUMO

BACKGROUND: The correlation and difference in T-cell phenotypes between peripheral blood lymphocytes (PBLs) and the tumor immune microenvironment (TIME) in patients with gastric cancer (GC) is not clear. We aimed to characterize the phenotypes of CD8+ T cells in tumor infiltrating lymphocytes (TILs) and PBLs in patients with different outcomes and to establish a useful survival prediction model. METHODS: Multiplex immunofluorescence staining and flow cytometry were used to detect the expression of inhibitory molecules (IMs) and active markers (AMs) in CD8+TILs and PBLs, respectively. The role of these parameters in the 3-year prognosis was assessed by receiver operating characteristic analysis. Then, we divided patients into two TIME clusters (TIME-A/B) and two PBL clusters (PBL-A/B) by unsupervised hierarchical clustering based on the results of multivariate analysis, and used the Kaplan-Meier method to analyze the difference in prognosis between each group. Finally, we constructed and compared three survival prediction models based on Cox regression analysis, and further validated the efficiency and accuracy in the internal and external cohorts. RESULTS: The percentage of PD-1+CD8+TILs, TIM-3+CD8+TILs, PD-L1+CD8+TILs, and PD-L1+CD8+PBLs and the density of PD-L1+CD8+TILs were independent risk factors, while the percentage of TIM-3+CD8+PBLs was an independent protective factor. The patients in the TIME-B group showed a worse 3-year overall survival (OS) (HR: 3.256, 95% CI 1.318-8.043, P = 0.006), with a higher density of PD-L1+CD8+TILs (P < 0.001) and percentage of PD-1+CD8+TILs (P = 0.017) and PD-L1+CD8+TILs (P < 0.001) compared to the TIME-A group. The patients in the PBL-B group showed higher positivity for PD-L1+CD8+PBLs (P = 0.042), LAG-3+CD8+PBLs (P < 0.001), TIM-3+CD8+PBLs (P = 0.003), PD-L1+CD4+PBLs (P = 0.001), and LAG-3+CD4+PBLs (P < 0.001) and poorer 3-year OS (HR: 0.124, 95% CI 0.017-0.929, P = 0.015) than those in the PBL-A group. In our three survival prediction models, Model 3, which was based on the percentage of TIM-3+CD8+PBLs, PD-L1+CD8+TILs and PD-1+CD8+TILs, showed the best sensitivity (0.950, 0.914), specificity (0.852, 0.857) and accuracy (κ = 0.787, P < 0.001; κ = 0.771, P < 0.001) in the internal and external cohorts, respectively. CONCLUSION: We established a comprehensive and robust survival prediction model based on the T-cell phenotype in the TIME and PBLs for GC prognosis.


Assuntos
Linfócitos T CD8-Positivos , Neoplasias Gástricas , Humanos , Antígeno B7-H1/metabolismo , Receptor Celular 2 do Vírus da Hepatite A/metabolismo , Neoplasias Gástricas/patologia , Receptor de Morte Celular Programada 1/metabolismo , Prognóstico , Linfócitos do Interstício Tumoral , Microambiente Tumoral
14.
Opt Express ; 31(23): 37703-37721, 2023 Nov 06.
Artigo em Inglês | MEDLINE | ID: mdl-38017895

RESUMO

Sensitivity to weather conditions is the principal limitation of free-space optical communication. However, for the scattering based ultraviolet (UV) non-line-of-sight (NLOS) communication, the atmospheric scattering effect functions as an attenuation factor and potentially as a performance enhancer. To investigate the UV NLOS transmission coverage under different weather conditions, we employ the Mie Theory in conjunction with classical aerosol and hydrometeor particle models to estimate the absorption coefficient, the scattering coefficient, and the scattering phase function. We then use these atmospheric parameters combined with a range estimation model to determine the coverage of the UV NLOS communication for specified path loss. Simulation results reveal that in non-precipitating weather, poorer visibility correlates with broader coverage. In foggy conditions, the coverage range in light fog exceeds that in fog-free environments; however, as fog intensity increases, the coverage range decreases. Rain enhances the coverage range; and heavier precipitation results in a larger coverage area.

15.
Opt Express ; 31(20): 33435-33448, 2023 Sep 25.
Artigo em Inglês | MEDLINE | ID: mdl-37859126

RESUMO

Due to a great many superior features of infrared light communication (ILC), like high capacity and strong privacy, ILC is considered a potential candidate for serving the high demands of beyond fifth-generation/sixth-generation (B5G/6 G) communication systems. However, the terminal's limited field-of-view (FOV) induces great difficulty in establishing line-of-sight (LoS) link between the transceiver and the terminal. In this paper, we propose a wide-FOV auto-coupling optical antenna system that utilizes a wide-FOV telecentric lens to collect incident infrared beams and automatically couple them into a specific single-mode-fiber (SMF) channel of fiber array and optical switch. The performance of this optical antenna system is assessed through simulation and manual alignment operation, and validated by automatic alignment results. A coupling loss of less than 10.6 dB within a FOV of 100° for both downstream and upstream beams in C band is demonstrated by the designed system. Furthermore, we establish a bidirectional optical wireless communications (OWC) system employing this antenna and a fiber-type modulating retro-reflector (MRR) system in the terminal. Both 10-Gbps on-off keying (OOK) downstream and upstream transmissions are successfully realized with the FOV of up to 100° in C band where the measured bit-error-rate (BER) is lower than 3.8 × 10-3. To the best of our knowledge, this is a brand-new auto-coupling optical antenna system with the largest FOV in ILC automatic alignment works in terminals that have ever been reported.

16.
Anal Biochem ; 676: 115234, 2023 09 01.
Artigo em Inglês | MEDLINE | ID: mdl-37422060

RESUMO

Abnormal expression of carcinoembryonic antigen (CEA) can be used for early diagnosis of various cancers (e.g. colorectal cancer, cervical carcinomas, and breast cancer). In this work, using l-cysteine-ferrocene-ruthenium nanocomposites (L-Cys-Fc-Ru) to immobilize secondary antibody (Ab2) and Au nanoparticles (NPs) as the substrate to ensure accurate capture of primary antibody (Ab1), a signal-on sandwich-like biosensor was constructed in the presence of CEA. Specifically, Ru nanoassemblies (NAs) were first prepared by a facile one-step solvothermal approach as signal amplifiers for the electrical signal of Fc. Based on specific immune recognition, as the increase of CEA concentration, the content of L-Cys-Fc-Ru-Ab2 captured on the electrode surface also increased, thus the signal of Fc gradually increased. Therefore, the quantitative detection of CEA can be realized according to the peak current of Fc. After a series of experiments, it was found that the biosensor has a wide detection range from 1.0 pg mL-1 to 100.0 ng mL-1 and a low detection limit down to 0.5 pg mL-1, as well as good selectivity, repeatability and stability. Furthermore, satisfactory results were also obtained for the determination of CEA in serums, which were comparable to commercial electrochemiluminescence (ECL) method. The developed biosensor shows great potential in clinical applications.


Assuntos
Técnicas Biossensoriais , Neoplasias da Mama , Nanopartículas Metálicas , Humanos , Feminino , Antígeno Carcinoembrionário , Ouro/química , Nanopartículas Metálicas/química , Imunoensaio/métodos , Técnicas Eletroquímicas/métodos , Técnicas Biossensoriais/métodos , Limite de Detecção
17.
Inorg Chem ; 62(2): 823-829, 2023 Jan 16.
Artigo em Inglês | MEDLINE | ID: mdl-36602526

RESUMO

Hybrid organic-inorganic metal halide (OIMH) perovskites are regarded as potential photoluminescent (PL) materials and have attracted intensive attention. Here, we select 1-methylpiperazine as an organic component and successfully obtain a two-dimensional (2D) Ge-based OIMH perovskite, (1-mpz)GeBr4. It features a 2D layered structure composed of distorted [GeBr6]4- octahedra with organic (C5H14N2)2+ located between the layers. (1-mpz)GeBr4 exhibits strong orange color under ultraviolet (UV) light and possesses good PL stability for over 2 months. The photoluminescence quantum efficiency is measured to be 7.15% at room temperature, which is the largest among all reported low-dimensional Ge-based perovskites. Experimental measurements, combined with first-principles calculations, reveal that its PL property is attributed to self-trapped excitons (STEs) from [GeBr6]4- groups. From the deduced structure-property relationship, Ge-based OIMH PL perovskites with good stability and high PL efficiency can be expected.

18.
Phys Chem Chem Phys ; 25(42): 28871-28884, 2023 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-37853798

RESUMO

The molecular mechanism of a Cu-catalysed coupling reaction was theoretically studied using density functional theory (DFT) and the complete active space self-consistent field method followed by the second-order perturbation theory (CASSCF/CASPT2) to investigate the effects of the strong electron correlation of the Cu centre on the reaction profile. Both DFT and CASSCF/CASPT2 calculations showed that the catalytic cycle proceeds via an oxidative addition (OA) reaction, followed by a reductive elimination (RE) reaction, where OA is the rate-determining step. Although the DFT-calculated activation energies of the OA and RE steps are highly dependent on the choice of functionals, the CASSCF/CASPT2 results are less affected by the choice of DFT-optimised geometries. Therefore, with a careful assessment based on the CASSCF/CASPT2 single-point energy evaluation, an optimal choice of the DFT geometry is of good qualitative use for energetics at the CASPT2 level of theory. Based on the changes in the electron populations of the 3d orbitals during the OA and RE steps, the characteristic features of the DFT-calculated electronic structure were qualitatively consistent with those calculated using the CASSCF method. Further electronic structure analysis by the natural orbital occupancy of the CASSCF wavefunction showed that the ground state is almost single-reference in this system and the strong electron correlation effect of the Cu centre can be dealt with using the MP2 or CCSD method, too. However, the slightly smaller occupation numbers of the 3dπ orbital in the course of reactions suggested that the electron correlation effect of the Cu(III) centre appears through the interaction between the 3dπ orbital and the C-I antibonding σ* orbital in the OA step, and between the 3dπ orbital and the Cu-C antibonding σ* orbital in the RE step.

19.
J Phys Chem A ; 127(8): 1975-1987, 2023 Mar 02.
Artigo em Inglês | MEDLINE | ID: mdl-36799901

RESUMO

We develop a multireference quantum embedding model to investigate a recent experimental observation of the isomerization of vibrationally excited CO molecules on a NaCl(100) surface [Science 2020, 367, 175-178]. To explore this mechanism, we built a reduced potential energy surface of CO interacting with NaCl(100) using a second-order multireference perturbation theory, modeling the adsorbate-surface interaction with our previously developed active space embedding theory (ASET). We considered an isolated CO molecule on NaCl(100) and a high-coverage CO monolayer (1/1), and for both we generated potential energy surfaces parametrized by the CO stretching, adsorption, and inversion coordinates. These surfaces are used to determine stationary points and adsorption energies and to perform a vibrational analysis of the states relevant to the inversion mechanism. We found that for near-equilibrium bond lengths, CO adsorbed in the C-down configuration is lower in energy than in the O-down configuration. Stretching of the C-O bond reverses the energetic order of these configurations, supporting the accepted isomerization mechanism. The vibrational constants obtained from these potential energy surfaces show a small (< 10 cm-1) blue- and red-shift for the C-down and O-down configurations, respectively, in agreement with experimental assignments and previous theoretical studies. Our vibrational analysis of the monolayer case suggests that the O-down configuration is energetically more stable than the C-down one beyond the 16th vibrational excited state of CO, a value slightly smaller than the one from quasi-classical trajectory simulations (22nd) and consistent with the experiment. Our analysis suggests that CO-CO interactions in the monolayer play an important role in stabilizing highly vibrationally excited states in the O-down configuration and reducing the barrier between the C-down and O-down geometries, therefore playing a crucial role in the inversion mechanism.

20.
Entropy (Basel) ; 25(1)2023 Jan 16.
Artigo em Inglês | MEDLINE | ID: mdl-36673320

RESUMO

Due to its simple structure and lack of moving parts, the supersonic air ejector has been widely applied in the fields of machinery, aerospace, and energy-saving. The performance of the ejector is influenced by the flow channel structure and the velocity of the jet, thus the confined jet is an important limiting factor for the performance of the supersonic air ejector. In order to investigate the effect of the confined jet on the performance of the ejector, an air ejector with a rectangular section was designed. The effects of the section width (Wc) on the entrainment ratio, velocity distribution, turbulent kinetic energy distribution, Mach number distribution, and vorticity distribution of the rectangular section air ejector were studied numerically. The numerical results indicated that the entrainment ratio of the rectangular section air ejector increased from 0.34 to 0.65 and the increment of the ER was 91.2% when the section width increased from 1 mm to 10 mm. As Wc increased, the region of the turbulent kinetic energy gradually expanded. The energy exchange between the primary fluid and the secondary fluid was mainly in the form of turbulent diffusion in the mixing chamber. In addition to Wc limiting the fluid flow in the rectangular section air ejector, the structure size of the rectangular section air ejector in the XOY plane also had a limiting effect on the internal fluid flow. In the rectangular section air ejector, the streamwise vortices played an important role in the mixing process. The increase of Wc would increase the distribution of the streamwise vortices in the constant-area section. Meanwhile, the distribution of the spanwise vortices would gradually decrease.

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