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1.
J Am Chem Soc ; 146(17): 12215-12224, 2024 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-38629769

RESUMO

We report the construction of frustrated Lewis pairs (FLPs) in a metal-organic framework (MOF), where both Lewis acid (LA) and Lewis base (LB) are fixed to the backbone. The anchoring of a tritopic organoboron linker as LA and a monotopic linker as LB to separate metal oxide clusters in a tetrahedron geometry allows for the precise control of distance between them. As the type of monotopic LB linker varies, pyridine, phenol, aniline, and benzyl alcohol, a series of 11 FLPs were constructed to give fixed distances of 7.1, 5.5, 5.4, and 4.8 Å, respectively, revealed by 11B-1H solid-state nuclear magnetic resonance spectroscopy. Keeping LA and LB apart by a fixed distance makes it possible to investigate the electrostatic effect by changing the functional groups in the monotopic LB linker, while the LA counterpart remains unaffected. This approach offers new chemical environments of the active site for FLP-induced catalysis.

2.
J Am Chem Soc ; 146(12): 8688-8696, 2024 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-38482699

RESUMO

Carbocations play a pivotal role as reactive intermediates in zeolite-catalyzed methanol-to-hydrocarbon (MTH) transformations. However, the interaction between carbocations and water vapor and its subsequent effects on catalytic performance remain poorly understood. Using micro-magnetic resonance imaging (µMRI) and solid-state NMR techniques, this work investigates the hydrophilic behavior of cyclopentenyl cations within ZSM-5 pores under vapor conditions. We show that the polar cationic center of cyclopentenyl cations readily initiates water nucleus formation through water molecule capture. This leads to an inhomogeneous water adsorption gradient along the axial positions of zeolite, correlating with the spatial distribution of carbocation concentrations. The adsorbed water promotes deprotonation and aromatization of cyclopentenyl cations, significantly enhancing the aromatic product selectivity in MTH catalysis. These results reveal the important influence of adsorbed water in modulating the carbocation reactivity within confined zeolite pores.

3.
BMC Plant Biol ; 24(1): 70, 2024 Jan 24.
Artigo em Inglês | MEDLINE | ID: mdl-38263006

RESUMO

BACKGROUND: The genus Sanicula L. is a unique perennial herb that holds important medicinal values. Although the previous studies on Sanicula provided us with a good research basis, its taxonomic system and interspecific relationships have not been satisfactorily resolved, especially for those endemic to China. Moreover, the evolutionary history of this genus also remains inadequately understood. The plastid genomes possessing highly conserved structure and limited evolutionary rate have proved to be an effective tool for studying plant phylogeny and evolution. RESULTS: In the current study, we newly sequenced and assembled fifteen Sanicula complete plastomes. Combined with two previously reported plastomes, we performed comprehensively plastid phylogenomics analyses to gain novel insights into the evolutionary history of this genus. The comparative results indicated that the seventeen plastomes exhibited a high degree of conservation and similarity in terms of their structure, size, GC content, gene order, IR borders, codon bias patterns and SSRs profiles. Such as all of them displayed a typical quadripartite structure, including a large single copy region (LSC: 85,074-86,197 bp), a small single copy region (SSC: 17,047-17,132 bp) separated by a pair of inverted repeat regions (IRs: 26,176-26,334 bp). And the seventeen plastomes had similar IR boundaries and the adjacent genes were identical. The rps19 gene was located at the junction of the LSC/IRa, the IRa/SSC junction region was located between the trnN gene and ndhF gene, the ycf1 gene appeared in the SSC/IRb junction and the IRb/LSC boundary was located between rpl12 gene and trnH gene. Twelve specific mutation hotspots (atpF, cemA, accD, rpl22, rbcL, matK, ycf1, trnH-psbA, ycf4-cemA, rbcL-accD, trnE-trnT and trnG-trnR) were identified that can serve as potential DNA barcodes for species identification within the genus Sanicula. Furthermore, the plastomes data and Internal Transcribed Spacer (ITS) sequences were performed to reconstruct the phylogeny of Sanicula. Although the tree topologies of them were incongruent, both provided strong evidence supporting the monophyly of Saniculoideae and Apioideae. In addition, the sister groups between Saniculoideae and Apioideae were strongly suggested. The Sanicula species involved in this study were clustered into a clade, and the Eryngium species were also clustered together. However, it was clearly observed that the sections of Sanicula involved in the current study were not respectively recovered as monophyletic group. Molecular dating analysis explored that the origin of this genus was occurred during the late Eocene period, approximately 37.84 Ma (95% HPD: 20.33-52.21 Ma) years ago and the diversification of the genus was occurred in early Miocene 18.38 Ma (95% HPD: 10.68-25.28 Ma). CONCLUSION: The plastome-based tree and ITS-based tree generated incongruences, which may be attributed to the event of hybridization/introgression, incomplete lineage sorting (ILS) and chloroplast capture. Our study highlighted the power of plastome data to significantly improve the phylogenetic supports and resolutions, and to efficiently explore the evolutionary history of this genus. Molecular dating analysis explored that the diversification of the genus occurred in the early Miocene, which was largely influenced by the prevalence of the East Asian monsoon and the uplift of the Hengduan Mountains (HDM). In summary, our study provides novel insights into the plastome evolution, phylogenetic relationships, taxonomic framework and evolution of genus Sanicula.


Assuntos
Apiaceae , Sanicula , Filogenia , Plastídeos , Cloroplastos
4.
Phys Rev Lett ; 132(11): 116201, 2024 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-38563913

RESUMO

Intriguing topological polar structures in oxide nanofilms have drawn growing attention owing to their immense potential applications in nanoscale electronic devices. Here, we report a novel route to mechanically manipulate polar structures via flexoelectricity in wrinkled thin films. Our results present a flexoelectric polar transition from a nonpolar state to uniaxial polar stripes, biaxial meronlike or antimeronlike polar structures, and polar labyrinths by varying wrinkle morphologies. The evolution mechanisms and the outstanding mechanical tunability of these flexoelectric polar patterns were investigated theoretically and numerically. This strategy based on flexoelectricity for generating nontrivial polar structures will no longer rely on the superlattice structure and can be widely applicable to all centrosymmetric or noncentrosymmetric materials, providing a broader range of material and structure candidates for polar topologies.

5.
Chemistry ; 30(34): e202401006, 2024 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-38625163

RESUMO

Direct determination of the equilibrium adsorption and spectroscopic observation of adsorbent-adsorbate interaction is crucial to evaluate the olefin/paraffin separation performance of porous adsorbents. However, the experimental characterization of competitive adsorption of various adsorbates at atomic-molecular level in the purification of multicomponent gas mixtures is challenging and rarely conducted. Herein, solid-state NMR spectroscopy is employed to examine the effect of co-adsorbed guest adsorbates on the separation of ethylene/ethane mixtures on Mg-MOF-74, Zn-MOF-74 and UTSA-74. 1H MAS NMR facilitates the determination of equilibrium uptake and adsorption selectivity of ethylene/ethane in ternary mixtures. The co-adsorption of H2O and CO2 significantly leads to the degradation of ethylene uptake and ethylene/ethane selectivity. The detailed host-guest and guest-guest interactions are unraveled by 2D 1H-1H spin diffusion homo-nuclear correlation and static 25Mg NMR experiments. The experimental results verify H2O coordinated on open metal sites can supply a new adsorption site for ethylene and ethane. The effects of guest adsorbates on the adsorption capacity and adsorption selectivity of ethylene/ethane mixtures are in the following order: H2O>CO2>O2. This work provides a direct approach for exploring the equilibrium adsorption and detailed separation mechanism of multicomponent gas mixtures using MOFs adsorbents.

6.
Reprod Biomed Online ; 48(1): 103585, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-38016376

RESUMO

RESEARCH QUESTION: What are the proteomic and phosphoproteomic differences between the endometrium of women with recurrent pregnancy loss (RPL) and the endometrium of healthy control women during the proliferative and secretory phases of the menstrual cycle? DESIGN: In total, 54 endometrial samples were collected during the proliferative and secretory phases from women with RPL (n = 28) and healthy controls (n = 26). Comprehensive proteomic and phosphoproteomic analyses were conducted using label-free liquid chromatography-tandem mass spectrometry (n = 44), and verified through Western blotting (n = 10). Three comparison groups were established: total RPL endometrium versus total control endometrium; RPL proliferative endometrium versus control proliferative endometrium; and RPL secretory endometrium versus control secretory endometrium. RESULTS: Differentially expressed proteins and differentially phosphorylated proteins were identified in the three comparison groups. Combining pathway enrichment, network analysis and soft clustering analysis, the insulin/cyclic nucleotide signalling pathway and AMPK/mTOR signalling pathway were identified as the major contributors to the aberration of RPL endometrium. Western blotting verified altered expression of four proteins: cAMP-dependent protein kinase type I-ß regulatory subunit, adenylate cyclase type 3, 5'-AMP-activated protein kinase catalytic subunit α-2 and phosphatidate phosphatase LPIN2. CONCLUSIONS: This exploratory study provides insights into the differentiated protein expression and phosphorylation profiles of the endometrium of women with RPL in both the proliferative and sectretory phases of the menstrual cycle. The results highlight potential proteins associated with the pathogenesis of RPL that may serve as potential indicators for RPL. The findings contribute to the identification of potential targets for RPL treatment as well as its pathogenesis.


Assuntos
Aborto Habitual , Insulina , Gravidez , Humanos , Feminino , Fosforilação , Proteômica/métodos , Endométrio/metabolismo , Aborto Habitual/patologia , Serina-Treonina Quinases TOR/metabolismo
7.
Cell Biol Int ; 48(5): 726-736, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38439187

RESUMO

Cellular senescence is an irreversible cell-cycle arrest in response to a variety of cellular stresses, which contribute to the pathogenesis of a variety of age-related degenerative diseases. However, effective antisenescence strategies are still lacking. Drugs that selectively target senescent cells represent an intriguing therapeutic strategy to delay aging and age-related diseases. Thus, we thought to investigate the effects of dihydroartemisinin (DHA) on senescent cells and elucidated its mechanisms underlying aging. Stress-induced premature senescence (SIPS) model was built in NIH3T3 cells using H2O2 and evaluated by ß-galactosidase staining. Cells were exposed to DHA and subjected to cellular activity assays including viability, ferroptosis, and autophagy. The number of microtubule-associated protein light-chain 3 puncta was detected by immunofluorescence staining. The iron content was assessed by spectrophotometer and intracellular reactive oxygen species (ROS) was measured by fluorescent probe dichlorodihydrofluorescein diacetate. We found that DHA triggered senescent cell death via ferroptosis. DHA accelerated ferritin degradation via promoting autophagy, increasing the iron contents, promoting ROS accumulation, thus leading to ferroptotic cell death in SIPS cells. In addition, autophagy inhibitor BafA1 preconditioning inhibited ferroptosis induced by DHA. Moreover, Atg5 silencing and autophagy inhibitor BafA1 preconditioning inhibited ferroptosis induced by DHA. We also revealed that the expression of p-AMP-activated protein kinase (AMPK) and p-mammalian target of rapamycin (mTOR) in senescent cells was downregulated. These results suggested that DHA may be a promising drug candidate for clearing senescent cells by inducing autophagy-dependent ferroptosis via AMPK/mTOR signaling pathway.


Assuntos
Proteínas Quinases Ativadas por AMP , Artemisininas , Ferroptose , Animais , Camundongos , Proteínas Quinases Ativadas por AMP/metabolismo , Autofagia , Senescência Celular , Peróxido de Hidrogênio/farmacologia , Ferro , Células NIH 3T3 , Espécies Reativas de Oxigênio/metabolismo , Transdução de Sinais , Serina-Treonina Quinases TOR/metabolismo
8.
Angew Chem Int Ed Engl ; 63(23): e202404633, 2024 Jun 03.
Artigo em Inglês | MEDLINE | ID: mdl-38509004

RESUMO

Solvent effects in catalytic reactions have received widespread attention as they can promote reaction rates and product selectivities by orders of magnitude. It is well accepted that the stable five-membered cyclic intermediates formed between the solvent molecules and Ti species are crucial to the alkene epoxidation in a heterogeneous Ti(IV)-H2O2 system. However, the direct spectroscopic evidence of these intermediates is still missing and the corresponding reaction pathway for the alkene epoxidation remains unclear. By combining in situ 13C MAS NMR, two-dimensional (2D) 1H-13C heteronuclear correlation (HETCOR) NMR spectroscopy and theoretical calculations, the five-membered ring structures, where the protic solvents (ROH), and aprotic solvent (acetone), coordinate and stabilize the active Ti species, are identified for the first time over Ti-Beta/H2O2 system. Moreover, the role of these cyclic intermediates in the alkene epoxidation/hydration conversion is clarified. These results provide new insights into the solvent effect in liquid-phase epoxidation/hydration reactions over Ti(IV)-H2O2 system.

9.
Angew Chem Int Ed Engl ; 63(3): e202313974, 2024 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-37934010

RESUMO

Water is a ubiquitous component in heterogeneous catalysis over zeolites and can significantly influence the catalyst performance. However, the detailed mechanism insights into zeolite-catalyzed reactions under microscale aqueous environment remain elusive. Here, using multiple dimensional solid-state NMR experiments coupled with ultrahigh magic angle spinning technique and theoretical simulations, we establish a fundamental understanding of the role of water in benzene methylation over ZSM-5 zeolite under water vapor conditions. We show that water competes with benzene for the active sites of zeolite and facilitates the bimolecular reaction mechanism. The growth of water clusters induces a micro-hydrophobic effect in zeolite pores, which reorients benzene molecules and drives their interactions with surface methoxy species (SMS) on zeolite. We identify the formation and evolution of active SMS-Benzene complexes in a microscale aqueous environment and demonstrate that their accumulation in zeolite pores boosts benzene conversion and methylation.

10.
J Am Chem Soc ; 145(9): 5342-5352, 2023 Mar 08.
Artigo em Inglês | MEDLINE | ID: mdl-36812430

RESUMO

Zeolites are widely used as catalysts and adsorbents in the chemical industry, but their potential for electronic devices has been stunted to date, as they are commonly recognized as electronic insulators. Here, we have for the first time demonstrated that Na-type ZSM-5 zeolites are ultrawide-direct-band-gap semiconductors based on optical spectroscopy, variable-temperature current-voltage characteristics, and photoelectric effect as well as electronic structure theoretical calculations and further unraveled the band-like charge transport mechanism in electrically conductive zeolites. The increase in charge-compensating Na+ cations in Na-ZSM-5 decreases the band gap and affects its density of states, shifting the Fermi level close to the conduction band. Remarkably, the semiconducting Na-ZSM-5 zeolites have been first applied for constructing electrically transduced sensors that can sense trace-level (77 ppb) ammonia with unprecedentedly high sensitivity, negligible cross-sensitivity, and high stability under moisture ambient conditions compared with conventional semiconducting materials and conductive metal-organic frameworks (MOFs). The charge density difference shows that the massive electron transfer between NH3 molecules and Na+ cations ascribed to Lewis acid sites enables electrically transduced chemical sensing. This work opens a new era of zeolites in applications of sensing, optics, and electronics.

11.
Hum Brain Mapp ; 44(6): 2142-2157, 2023 04 15.
Artigo em Inglês | MEDLINE | ID: mdl-36617994

RESUMO

Anaesthesia combined with functional neuroimaging provides a powerful approach for understanding the brain mechanisms of consciousness. Although propofol is used ubiquitously in clinical interventions that reversibly suppress consciousness, it shows large inter-individual variability, and the brain bases of this variability remain poorly understood. We asked whether three networks key to conscious cognition-the dorsal attention (DAN), executive control (ECN), and default mode (DMN)-underlie responsiveness variability under anaesthesia. Healthy participants (N = 17) were moderately anaesthetized during narrative understanding and resting-state conditions inside the Magnetic Resonance Imaging scanner. A target detection task measured behavioural responsiveness. An independent behavioural study (N = 25) qualified the attention demands of narrative understanding. Then, 30% of participants were unaffected in their response times, thus thwarting a key aim of anaesthesia-the suppression of behavioural responsiveness. Individuals with stronger functional connectivity within the DAN and ECN, between them, and to the DMN, and with larger grey matter volume in frontal regions were more resilient to anaesthesia. For the first time, we show that responsiveness variability during propofol anaesthesia relates to inherent differences in brain structure and function of the frontoparietal networks, which can be predicted prior to sedation. Results highlight novel markers for improving awareness monitoring during clinical anaesthesia.


Assuntos
Anestesia , Propofol , Humanos , Propofol/farmacologia , Encéfalo/diagnóstico por imagem , Encéfalo/fisiologia , Estado de Consciência/fisiologia , Cognição , Mapeamento Encefálico , Imageamento por Ressonância Magnética/métodos , Vias Neurais/diagnóstico por imagem , Função Executiva
12.
BMC Plant Biol ; 23(1): 70, 2023 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-36726056

RESUMO

The subgenus Rhizirideum in the genus Allium consists of 38 species worldwide and forms five sections (A. sect. Rhizomatosa, A. sect. Tenuissima, A. sect. Rhizirideum, A. sect. Eduardia, and A. sect. Caespitosoprason), A. sect. Caespitosoprason being merged into A. sect. Rhizomatosa recently. Previous studies on this subgenus mainly focused on separate sections. To investigate the inter-section and inter-subgenera phylogenetic relationships and adaptive evolution of A. subg. Rhizirideum, we selected thirteen representative species, which cover five sections of this subgenus and can represent four typical phenotypes of it. We conducted the comparative plastome analysis with our thirteen plastomes. And phylogenetic inferences with CDSs and complete sequences of plastomes of our thirteen species and another fifty-four related species were also performed. As a result, the A. subg. Rhizirideum plastomes were relatively conservative in structure, IR/SC borders, codon usage, and repeat sequence. In phylogenetic results, the inter-subgenera relationships among A. subg. Rhizirideum and other genus Allium subgenera were generally similar to the previous reports. In contrast, the inter-section relationships within our subgenus A. subg. Rhizirideum were newly resolved in this study. A. sect. Rhizomatosa and A. sect. Tenuissima were sister branches, which were then clustered with A. sect. Rhizirideum and A. sect. Eduardia successively. However, Allium Polyrhizum Turcz. ex Regel, type species of A. sect. Caespitosoprason, was resolved as the basal taxon of A. subg. Rhizirideum. Allium siphonanthum J. M. Xu was also found in clade A. subg. Cyathophora instead of clade A. subg. Rhizirideum. The selective pressure analysis was also conducted, and most protein-coding genes were under purifying selection. At the same time, just one gene, ycf2, was found under positive selection, and another three genes (rbcL, ycf1a, ycf1b) presented relaxed selection, which were all involved in the photosynthesis. The low temperature, dry climate, and high altitude of the extreme habitats where A. subg. Rhizirideum species grow might impose intense natural selection forces on their plastome genes for photosynthesis. In summary, our research provides new insights into the phylogeny and adaptive evolution of A. subg. Rhizirideum. Moreover, we suggest that the positions of the A. subg. Rhizirideum species A. polyrhizum and A. siphonanthum should be reconsidered.


Assuntos
Allium , Amaryllidaceae , Genomas de Plastídeos , Allium/genética , Amaryllidaceae/genética , Filogenia , Sequências Repetitivas de Ácido Nucleico , Evolução Molecular
13.
Small ; 19(30): e2302509, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-37026662

RESUMO

Aerogels have provided a significant platform for passive radiation-enabled thermal regulation, arousing extensive interest due to their capabilities of radiative cooling or heating. However, there still remains challenge of developing functionally integrated aerogels for sustainable thermal regulation in both hot and cold environment. Here, Janus structured MXene-nanofibrils aerogel (JMNA) is rationally designed via a facile and efficient way. The achieved aerogel presents the characteristic of high porosity (≈98.2%), good mechanical strength (tensile stress of ≈2 MPa, compressive stress of ≈115 kPa), and macroscopic shaping property. Based on the asymmetric structure, the JMNA with switchable functional layers can alternatively enable passive radiative heating and cooling in winter and summer, respectively. As a proof of concept, JMNA can function as a switchable thermal-regulated roof to effectively enable the inner house model to maintain >25 °C in winter and <30 °C in hot summer. This design of Janus structured aerogels with compatible and expandable capabilities is promising to widely benefit the low-energy thermal regulation in changeable climate.

14.
Gynecol Oncol ; 170: 25-31, 2023 03.
Artigo em Inglês | MEDLINE | ID: mdl-36608384

RESUMO

OBJECTIVE: To assess the actual clinical application of poly (adenosine diphosphate-ribose) polymerase inhibitor (PARPi) maintenance therapy in Chinese patients with recurrent ovarian cancer, and to explore prognostic factors associated with progression-free survival (PFS). METHODS: We retrospectively assessed real-world clinical data from our hospital using the inclusion and exclusion criteria of representative randomized controlled trials, analyzed the prognosis, and performed univariate and multivariate analyses of prognostic factors. RESULTS: Between 2019 and 2022, the proportion of platinum-sensitive recurrence ovarian cancer patients who received PARPi maintenance therapy increased to 29.6%, 53.3%, 43.8% and 62.2%, respectively, each year. A total of 48 patients were included in the prognostic analysis, of which 32 and 16 received olaparib and niraparib, respectively. Using the criteria of the Study19 and SOLO2 studies, the olaparib group in our patients had coincidence rates of 56.3% and 18.8%, respectively. Using the criteria of the NOVA and NORA studies, the niraparib group had coincidence rates of 31.3% and 37.5%, respectively. Median PFS was 26.1 months (95% CI 20.2-32.1). Response to primary therapy was an independent prognostic factor for PFS (relative risk, 3.248; 95% CI 1.081-9.757, P = 0.036). CONCLUSIONS: PARPi maintenance therapy was also effective in real world applications. Complete response (CR) to primary therapy was an independent factor favorably affecting PFS. Therefore, primary treatment choices aimed at optimal cytoreduction during primary surgery and improving the CR rate should still be considered, which positively affects the long-term prognosis of patients in the new treatment mode.


Assuntos
Neoplasias Ovarianas , Humanos , Feminino , Neoplasias Ovarianas/tratamento farmacológico , Inibidores de Poli(ADP-Ribose) Polimerases/uso terapêutico , Estudos Retrospectivos , Recidiva Local de Neoplasia/tratamento farmacológico , Carcinoma Epitelial do Ovário/tratamento farmacológico
15.
Br J Clin Pharmacol ; 89(7): 2309-2315, 2023 07.
Artigo em Inglês | MEDLINE | ID: mdl-36740817

RESUMO

We present 3 patients diagnosed with rhabdomyolysis 1-6 months after the initiation of concomitant rosuvastatin and ticagrelor medication. A literature review and Food and Drug Administration adverse event reporting system revealed >40 reports of rhabdomyolysis during concomitant ticagrelor and rosuvastatin, including 3 with a fatal outcome. We show that ticagrelor inhibits breast cancer resistance protein-, organic anion transporting polypeptide (OATP) 1B1-, 1B3- and 2B1-mediated transport of rosuvastatin in vitro with half-maximal unbound inhibitory concentrations of 0.36, 4.13, 7.5 and 3.26 µM, respectively. A static drug interaction model predicted that ticagrelor may inhibit intestinal breast cancer resistance protein and thus increase rosuvastatin plasma exposure 2.1-fold, whereas the OATP-mediated hepatic uptake of rosuvastatin should not be inhibited due to relatively low portal ticagrelor concentrations. Taken together, concomitant use of ticagrelor with rosuvastatin may increase the systemic exposure to rosuvastatin and the risk of rosuvastatin-induced rhabdomyolysis. Further studies are warranted to investigate the potential pharmacokinetic interaction between ticagrelor and rosuvastatin in humans.


Assuntos
Neoplasias da Mama , Transportadores de Ânions Orgânicos , Rabdomiólise , Estados Unidos , Humanos , Feminino , Rosuvastatina Cálcica/efeitos adversos , Rosuvastatina Cálcica/farmacocinética , Ticagrelor/efeitos adversos , Membro 2 da Subfamília G de Transportadores de Cassetes de Ligação de ATP , Proteínas de Neoplasias/metabolismo , Interações Medicamentosas , Transportadores de Ânions Orgânicos/metabolismo , Rabdomiólise/induzido quimicamente , Neoplasias da Mama/tratamento farmacológico
16.
Inorg Chem ; 62(8): 3464-3473, 2023 Feb 27.
Artigo em Inglês | MEDLINE | ID: mdl-36791390

RESUMO

A hydrothermal method was used to synthesize two highly stable Zn(II) metal-organic frameworks (MOFs), namely, [Zn2(L)2(HIPA)]n (1) and [Zn9(L)6(BTEC)3(H2O)4·6H2O]n (2) (HL = 3-amino-1H-1,2,4-triazole, H2HIPA = 5-hydroxyisophthalic acid, H4BTEC = benzene-1,2,4,5-tetracarboxylic acid). The physicochemical properties of 1 and 2 were characterized using a range of analytical techniques. The scanning electron microscopy images confirmed the stability of the MOFs under heating at 120 °C for 12 h. Following their preparation, the two MOFs were used as catalysts in the grafting of poly(ε-caprolactone) on wood nanofibers (WNFs) by means of a homogeneous ring-opening polymerization protocol in an ionic liquid. The grafting ratio achieved using catalyst 1 was higher than that achieved for catalyst 2, wherein a maximum of 92.43% was obtained using the former. Under comparable reaction conditions, the grafting ratio of 1 was found to be significantly higher than those achieved using 4-dimethylamino pyridine, Sn(Oct)2, and UiO-67 catalysts. In addition, fluorescence emission was detected from the residual catalysts present in the products. The calculated electrostatic potentials and average local ionization energies indicated that the grafting of ε-caprolactone on the WNFs follows a "coordination-insertion" mechanism. Overall, these two new and efficient MOF catalysts have the potential to replace highly toxic traditional catalysts in polymerization reactions. The grafted cellulose material with fluorescence emission may also be suitable for use in biomedical applications.

18.
Med Sci Monit ; 29: e938485, 2023 Jan 12.
Artigo em Inglês | MEDLINE | ID: mdl-36632023

RESUMO

BACKGROUND Plantar pressure analysis is widely used in the study of knee osteoarthritis (KOA). The present study aimed to investigate the static and dynamic plantar pressure distribution in patients with different stages of unilateral KOA using the Footscan® platform system. MATERIAL AND METHODS We recruited 94 patients aged 61.75±7.23 years old with different stages of unilateral KOA for static and dynamic analysis using the Footscan® platform system. The static pressure (%) of the left, right, anterior, posterior, and the pelvic rotation (°) was assessed. The peak pressure (PP, kPa) was investigated in 10 areas of the foot: medial heel (MH), lateral heel (LH), midfoot (MF), first to fifth metatarsals (M1-M5), hallux (T1), and toes 2-5 (T2-5). The correlation between KOA stages and plantar pressure distributions was investigated. RESULTS The results revealed that static pressure on the unaffected side and pelvic rotation were positively correlated with KOA stages. In addition, there was a positive correlation between KOA stages and PP of M5, MF, and LH zones on the affected side and PP of M2, M3, and M4 zones on the unaffected side, and a negative correlation between KOA stages and PP of T1 and T2-5 zones on the affected side. CONCLUSIONS With the progression of KOA, static plantar pressure tends to distributed on the unaffected side, and the dynamic plantar pressure tends to be distributed laterally on both feet. The plantar pressure distributions in unilateral KOA patients are abnormal and are closely related to the severity of KOA.


Assuntos
Osteoartrite do Joelho , Humanos , Pessoa de Meia-Idade , Idoso , Marcha , Pressão , , Calcanhar
19.
BMC Ophthalmol ; 23(1): 16, 2023 Jan 10.
Artigo em Inglês | MEDLINE | ID: mdl-36627585

RESUMO

PURPOSE: Corneal collagen crosslinking (CXL) is an effective treatment for progressive keratoconus. Multiple CXL modalities are clinically available. The present study compared the 1 year outcomes of five types of CXL procedures for progressive keratoconus in a Chinese population using generalized estimating equations (GEE). METHODS: This retrospective study included 239 eyes in 171 patients with keratoconus who underwent CXL and were followed up for 1 year. Five CXL procedures were assessed, including Accelerated Transepithelial CXL, Iontophoresis CXL for 10 min, CXL plus phototherapeutic keratectomy (CXL-plus-PTK), High-Fluence Accelerated CXL, and Accelerated CXL. Patients treated with the Accelerated CXL procedure represented the reference group. Primary outcomes were visual acuity change, spherical equivalence, endothelial cell density, mean keratometry (Kmean), maximum keratometry (Kmax), minimum corneal thickness (MCT), and the ABCD Grading System, consisting of A (staging index for ARC; ARC = anterior radius of curvature), B (staging index for PRC, PRC = posterior radius of curvature), and C (staging index for MCT) values 1 year postoperatively compared to baseline. Secondary outcomes were corrected GEE comparisons from each procedure versus the Accelerated CXL group. RESULTS: The Accelerated Transepithelial CXL group had lower performance than the Accelerated CXL group according to Kmean and Kmax. The CXL-plus-PTK group performed significantly better than the reference group as reflected by Kmax (ß = -0.935, P = 0.03). However, the CXL-plus-PTK group did not perform as well for B and C, and the Iontophoresis CXL group performed better for C. CONCLUSIONS: The CXL-plus-PTK procedure was more effective than the Accelerated CXL procedure based on Kmax, and the Iontophoresis CXL procedure performed better on the C value based on the ABCD Grading System.


Assuntos
Ceratocone , Fotoquimioterapia , Humanos , Ceratocone/tratamento farmacológico , Fármacos Fotossensibilizantes/uso terapêutico , Fotoquimioterapia/métodos , Estudos Retrospectivos , Riboflavina/uso terapêutico , Seguimentos , Colágeno/uso terapêutico , Reagentes de Ligações Cruzadas/uso terapêutico , Raios Ultravioleta , Topografia da Córnea
20.
BMC Anesthesiol ; 23(1): 379, 2023 11 20.
Artigo em Inglês | MEDLINE | ID: mdl-37986138

RESUMO

BACKGROUND: Mechanical ventilation during general anesthesia may impair airway mucosal function. This study aimed to investigate the effect of pressure-controlled ventilation-volume guaranteed (PCV-VG) on bronchial mucus transport velocity (BTV) in patients during laparoscopic surgery for gynecological oncology compared with volume controlled ventilation (VCV). METHODS: 66 patients undergoing elective a laparoscopic surgery for gynecological oncology. The patients were randomized into two group receiving either PCV-VG or VCV. a drop of methylene blue was placed on the surface of the airway mucosa under the bronchoscopeand, then the distance the dye movement was measured after 2, 4, and 6 min. Outcomes were assessed at T0 (5 min after endotracheal intubation and before initiation of pneumoperitoneum), T1 and T2 (1 and 2 h after stabilization of pneumoperitoneum respectively). BTV at T0, T1 and T2 was the primary outcome. Secondary outcomes included heart rate (HR), mean arterial pressure (MAP), body temperature, end-tidal CO2 pressure (PETCO2), tidal volume(VT), peak inspiratory pressure (PIP), mean inspiratory pressure (Pmean), respiratory rate (RR), and dynamic compliance (CDyn) at T0, T1, and T2. RESULTS: 64 patients were included in the analysis. The median [interquartile range] BTV was significantly lower in VCV group at T1 and T2 that at T0 (P < 0.05). Furthermore, BTV was slightly reduced in PCV-VG compared with VCV. BTV in PCV-VG was significantly decreased at T2 compared with BTV at T0 (P < 0.05) and slightly decreased at T1 compared with T0(P > 0.05). Compared with the PCV-VG group, BTV in VCV group significantly decreased at T2 (P < 0.05). No participants experienced respiratory complications. CONCLUSIONS: PCV-VG is more suitable for patients undergoing laparoscopic surgery for gynecological oncology than VCV since it can protect mucociliary clearance function. TRIAL REGISTRATION: This trial is registered on https://www.chictr.org.cn/ in Chinese Clinical Trial Registry (ChiCTR.2200064564: Date of registration 11/10/2022).


Assuntos
Laparoscopia , Pneumoperitônio , Humanos , Respiração Artificial , Volume de Ventilação Pulmonar , Muco
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