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1.
J Comput Chem ; 45(19): 1630-1641, 2024 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-38539259

RESUMO

The synergistic regulation of the multi-functional sites on one receptor molecule with different cationic effectors for anion recognition is scarce to be well understood from the experiment and theory. In this work, a new anion receptor with three functional zones including ether hole, biurea and double bipyridine groups (EUPR) is designed expecting to enhance the chloride anion recognition together with a rational synthesis path being proposed based on four simple and mature organic reaction steps. The conformational structures of the designed receptor EUPR and the binding behaviors for three kinds of ions (Cl-, Na+, and Ag+) are deeply investigated by using density functional theoretical calculations. It is found that Cl- binding via the hydrogen bond interaction can be significantly enhanced and synergistically regulated by the two kinds of cations and the corresponding conformational changes of receptor EUPR. Especially, the conformational pre-organization of receptor caused by the encapsulation of sodium ion into ether hole is benefit to the binding for Cl- in both thermodynamics and kinetics. Na+ binding, in turn, can ever be enhanced by chloride anion, whereas it seems that Ag+ binding cannot always be enhanced by chloride anion, reflecting an electrical complementary matching and mutual enhancement effect for different counter ions. Moreover, solvent effect calculations indicate that EUPR may be an ideal candidate structure for Cl- recognition by strategy of counter ion enhancement in water. Additionally, a visual study of intermolecular noncovalent interaction (NCI) and molecular electrostatic potential (ESP) are used for the analysis on the nature of interactions between receptor and bound ions.

2.
Small ; 20(24): e2311174, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38174619

RESUMO

Modulating the coordination configuration of single Fe atom has been an efficient strategy to strengthen the redox dynamics for lithium-sulfur batteries (LSBs) but remains challenging. Herein, the single Fe atom is functioned with nitrogen and carbon atoms in the first shell, and simultaneously, oxidized sulfur (─SOx) in the second shell, which presents a lower antibonding state and well address the redox activity of sulfur cathodes. In the ternary-coordinated single Fe atom catalyst (FeN2C2-SOx-NC), the binary structure of FeN2C2 provides a lower Fe-S bonding strength and d-p orbital hybridization, which obviously optimizes the adsorption and desorption behavior of sulfur species during the reduction and oxidation reaction processes. Simultaneously, the ─SOx redistributes the electron density of the coordinating nitrogen atoms, which possesses high electron-withdrawing ability and develops electrocatalytic activity. As a result, the sulfur cathodes with FeN2C2-SOx-NC present an excellent high-rate cyclic performance, accompanied by a capacity decay rate of 0.08% per cycle for 500 cycles at 4.0 C. This study provides new insights for optimizing the redox dynamics of sulfur cathodes in LSBs at the atomic level.

3.
Langmuir ; 40(11): 5571-5589, 2024 Mar 19.
Artigo em Inglês | MEDLINE | ID: mdl-38440955

RESUMO

Polymer brushes have received great attention in recent years due to their distinctive properties and wide range of applications. The synthesis of polymer brushes typically employs surface-initiated atom transfer radical polymerization (SI-ATRP) techniques. To realize the control of the polymerization process in different environments, various SI-ATRP techniques triggered by different stimuli have been developed. This review focuses on the latest developments in different stimuli-triggered SI-ATRP methods, such as electrochemically mediated, photoinduced, enzyme-assisted, mechanically controlled, and organocatalyzed ATRP. Additionally, SI-ATRP technology triggered by a combination of multiple stimuli sources is also discussed. Furthermore, the applications of polymer brushes in lubrication, biological applications, antifouling, and catalysis are also systematically summarized and discussed. Despite the advancements in the synthesis of various types of 1D, 2D, and 3D polymer brushes via controlled radical polymerization, contemporary challenges remain in the quest for more efficient and straightforward synthetic protocols that allow for precise control over the composition, structure, and functionality of polymer brushes. We anticipate the readers could promote the understanding of surface functionalization based on ATRP-mediated polymer brushes and envision future directions for their application in surface coating technologies.

4.
Microb Cell Fact ; 23(1): 89, 2024 Mar 25.
Artigo em Inglês | MEDLINE | ID: mdl-38528536

RESUMO

BACKGROUND: Staphylococcus aureus and its single or mixed biofilm infections seriously threaten global public health. Phage therapy, which uses active phage particles or phage-derived endolysins, has emerged as a promising alternative strategy to antibiotic treatment. However, high-efficient phage therapeutic regimens have yet to be established. RESULTS: In this study, we used an enrichment procedure to isolate phages against methicillin-resistant S. aureus (MRSA) XN108. We characterized phage SYL, a new member of the Kayvirus genus, Herelleviridae family. The phage endolysin LysSYL was expressed. LysSYL demonstrated stability under various conditions and exhibited a broader range of efficacy against staphylococcal strains than its parent phage (100% vs. 41.7%). Moreover, dynamic live/dead bacterial observation demonstrated that LysSYL could completely lyse MRSA USA300 within 10 min. Scan and transmission electron microscopy revealed evident bacterial cell perforation and deformation. In addition, LysSYL displayed strong eradication activity against single- and mixed-species biofilms associated with S. aureus. It also had the ability to kill bacterial persisters, and proved highly effective in eliminating persistent S. aureus when combined with vancomycin. Furthermore, LysSYL protected BALB/c mice from lethal S. aureus infections. A single-dose treatment with 50 mg/kg of LysSYL resulted in a dramatic reduction in bacterial loads in the blood, liver, spleen, lungs, and kidneys of a peritonitis mouse model, which resulted in rescuing 100% of mice challenged with 108 colony forming units of S. aureus USA300. CONCLUSIONS: Overall, the data provided in this study highlight the strong therapeutic potential of endolysin LysSYL in combating staphylococcal infections, including mono- and mixed-species biofilms related to S. aureus.


Assuntos
Endopeptidases , Staphylococcus aureus Resistente à Meticilina , Infecções Estafilocócicas , Animais , Camundongos , Staphylococcus , Staphylococcus aureus , Fagos de Staphylococcus , Antibacterianos/farmacologia , Antibacterianos/uso terapêutico , Infecções Estafilocócicas/tratamento farmacológico , Infecções Estafilocócicas/microbiologia , Biofilmes
5.
Arterioscler Thromb Vasc Biol ; 43(2): 218-230, 2023 02.
Artigo em Inglês | MEDLINE | ID: mdl-36353991

RESUMO

BACKGROUND: Myocardial cell death is the hallmark of myocardial infarction. In the process of myocardial injury, platelets contribute to the pathogenesis by triggering intense inflammatory responses. Yet, it is still unclear if platelets regulate cardiomyocyte death directly, thereby exacerbating myocardial injury in myocardial infarction. METHODS: We describe a mechanism underlying the correlative association between platelets accumulation and myocardial cell death by using myocardial infarction mouse model and patient specimens. RESULTS: Myocardial infarction induces platelets internalization, resulting in the release of miR-223-3p, a platelet-enriched miRNA. By targeting the ACSL3, miR-223-3p delivered by internalized platelets cause the reduction of stearic acid-phosphatidylcholine in cardiomyocytes. The presence of stearic acid-phosphatidylcholine protects cardiomyocytes against ferroptosis. CONCLUSIONS: Our work reveals a novel mechanism of platelet-mediated myocardial injury, highlighting antiplatelet therapies could potentially represent a multimechanism treatment of myocardial infarction, and implying ferroptosis being considered as novel target for therapeutics.


Assuntos
Ferroptose , MicroRNAs , Infarto do Miocárdio , Camundongos , Animais , Plaquetas/metabolismo , Infarto do Miocárdio/metabolismo , MicroRNAs/genética , MicroRNAs/metabolismo , Morte Celular , Miócitos Cardíacos/metabolismo
6.
Inorg Chem ; 63(2): 1188-1196, 2024 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-38175718

RESUMO

Metal-organic frameworks (MOFs) with long persistent luminescence (LPL) have attracted extensive research attention from researchers due to their potential applications in information encryption, anticounterfeiting technology, and security logic. In contrast to short-lived fluorescent materials, LPL materials offer a visible response that can be easily distinguished by the naked eye, thereby facilitating a much clearer visualization. However, there are few reports on functional LPL MOF materials as probes. In this article, two amino-functional LPL MOFs (VB4-2D and VB4-1D) were synthesized. They both exhibited adjustable fluorescence and phosphorescence from blue to green and from cyan to green, respectively. Notably, the MOFs emitted bright and adjustable LPL upon the removal of the different radiation sources. The basic amino functional groups in the MOFs exhibited acid and ammonia sensitivity, and fluorescence and phosphorescence emission intensities can be burst and restored in two atmospheres, respectively, which can be cycled multiple times. Furthermore, LPL intensity undergoes switching between two different conditions as well, which can be visually discerned by the naked eye, enabling visual sensing of volatiles by LPL. This combination of photoluminescence and the visual LPL switching behavior of acids and bases in functional MOFs may provide an effective avenue for stimulus response, anticounterfeiting, and encryption applications.

7.
Phys Chem Chem Phys ; 2024 Jun 24.
Artigo em Inglês | MEDLINE | ID: mdl-38910568

RESUMO

This study introduces a new wide-bandgap graphene-like structure, denoted as C6BN, achieved by incorporating an eight-electron BN pair, substantially modifying its electronic properties. Utilizing extensive density functional calculations, we comprehensively analyzed the stability, electronic structure, mechanical properties, and optical-electrical characteristics of C6BN. Our investigations reveal the material's exceptional thermodynamic, mechanical, and dynamic stability. Notably, the calculated wide bandgap of 2.81 eV in C6BN, supported by analyses of energy levels, band structures, and density of states, positions it as a promising two-dimensional wide-bandgap semiconductor. Additionally, C6BN exhibits isotropic mechanical features, highlighting its inherent flexibility. Remarkably, our calculations indicate an ultra-low dielectric constant (k = 1.67) for C6BN, surpassing that of well-established third-generation semiconductors. Further exploration into the thermoelectric properties of C6BN demonstrates its promising performance, as evidenced by calculations of thermal conductivity (κ), power factor (P), and Seebeck coefficient (S). In summary, our findings underscore the significant potential of the proposed C6BN structure as a flexible two-dimensional material poised to drive future advancements in electronic and energy-related technologies.

8.
J Chem Phys ; 160(12)2024 Mar 28.
Artigo em Inglês | MEDLINE | ID: mdl-38526106

RESUMO

This study focuses on the recognition and isolation of fullerenes, which are crucial for further exploration of their physical and chemical properties. Our goal is to investigate the potential recognition of the D5h-C70 fullerene using crown-shaped metal compositions through density functional theory calculations. We assess the effectiveness of fullerene C70 recognition by studying the binding energy. Additionally, various analyses were conducted, including natural bond order charge analysis and reduced density gradient analysis, to understand the interaction mechanism between the host and guest molecules. These investigations provide valuable insights into the nature of the interaction and the stability of the host-guest system. To facilitate the release of the fullerene guest molecule, the vis-NIR spectra were simulated for the host-guest structures. This analysis offers guidance on the specific wavelengths that can be utilized to release the fullerene guest from the host-guest structures. Overall, this work proposes a new strategy for the effective recognition of various fullerene molecules and their subsequent release from host-guest systems. These findings could potentially be applied in assemblies involving fullerenes, advancing their practical applications.

9.
Cell Mol Biol Lett ; 29(1): 3, 2024 Jan 03.
Artigo em Inglês | MEDLINE | ID: mdl-38172650

RESUMO

BACKGROUND: Circular RNAs are enriched in cardiac tissue and play important roles in the pathogenesis of heart diseases. In this study, we aimed to investigate the regulatory mechanism of a conserved heart-enriched circRNA, circPan3, in cardiac hypertrophy. METHODS: Cardiac hypertrophy was induced by isoproterenol. The progression of cardiomyocyte hypertrophy was assessed by sarcomere organization staining, cell surface area measurement, and expression levels of cardiac hypertrophy markers. RNA interactions were detected by RNA pull-down assays, and methylated RNA immunoprecipitation was used to detect m6A level. RESULTS: The expression of circPan3 was downregulated in an isoproterenol-induced cardiac hypertrophy model. Forced expression of circPan3 attenuated cardiomyocyte hypertrophy, while inhibition of circPan3 aggravated cardiomyocyte hypertrophy. Mechanistically, circPan3 was an endogenous sponge of miR-320-3p without affecting miR-320-3p levels. It elevated the expression of HSP20 by endogenously interacting with miR-320-3p. In addition, circPan3 was N6-methylated. Stimulation by isoproterenol downregulated the m6A eraser ALKBH5, resulting in N6-methylation and destabilization of circPan3. CONCLUSIONS: Our research is the first to report that circPan3 has an antihypertrophic effect in cardiomyocytes and revealed a novel circPan3-modulated signalling pathway involved in cardiac hypertrophy. CircPan3 inhibits cardiac hypertrophy by targeting the miR-320-3p/HSP20 axis and is regulated by ALKBH5-mediated N6-methylation. This pathway could provide potential therapeutic targets for cardiac hypertrophy.


Assuntos
MicroRNAs , RNA Circular , Humanos , RNA Circular/genética , RNA Circular/metabolismo , MicroRNAs/genética , MicroRNAs/metabolismo , Isoproterenol , Cardiomegalia/genética , Cardiomegalia/patologia , Miócitos Cardíacos/metabolismo
10.
Ecotoxicol Environ Saf ; 278: 116400, 2024 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-38718725

RESUMO

Evidence increasingly suggests molybdenum exposure at environmental levels is still associated with adverse human health, emphasizing the necessity to establish a more protective reference dose (RfD). Herein, we conducted a study measuring 15 urinary metals and 30 clinical health indicators in 2267 participants residing near chemical enterprises across 11 Chinese provinces to investigate their relationships. The kidney and cystatin-C emerged as the most sensitive organ and critical effect indicator of molybdenum exposure, respectively. Odds of cystatin-C-defined chronic kidney disease (CKD) in the highest quantile of molybdenum exposure significantly increased by 133.5% (odds ratio [OR]: 2.34, 95% CI: 1.78, 3.11) and 75.8% (OR: 1.76, 95% CI: 1.24, 2.49) before and after adjusting for urinary 14 metals, respectively. Intriguingly, cystatin-C significantly mediated 15.9-89.5% of molybdenum's impacts on liver and lung function, suggesting nephrotoxicity from molybdenum exposure may trigger hepatotoxicity and pulmonary toxicity. We derived a new RfD for molybdenum exposure (0.87 µg/kg-day) based on cystatin-C-defined estimated glomerular filtration rate by employing Bayesian Benchmark Dose modeling analysis. This RfD is significantly lower than current exposure guidance values (5-30 µg/kg-day). Remarkably, >90% of participants exceeded the new RfD, underscoring the significant health impacts of environmental molybdenum exposure on populations in industrial regions of China.


Assuntos
Molibdênio , Molibdênio/urina , Molibdênio/toxicidade , Molibdênio/análise , Humanos , China/epidemiologia , Feminino , Masculino , Adulto , Pessoa de Meia-Idade , Exposição Ambiental/estatística & dados numéricos , Exposição Ambiental/análise , Cistatina C , Medição de Risco , Poluentes Ambientais/urina , Poluentes Ambientais/análise , Adulto Jovem , Teorema de Bayes , Insuficiência Renal Crônica/epidemiologia , Insuficiência Renal Crônica/induzido quimicamente , Idoso , Indústria Química , Rim/efeitos dos fármacos , Taxa de Filtração Glomerular/efeitos dos fármacos
11.
J Am Chem Soc ; 2023 Nov 03.
Artigo em Inglês | MEDLINE | ID: mdl-37922470

RESUMO

Fullerene transformation emerges as a powerful route to construct defect-rich carbon electrocatalysts, but the carbon bond breakage and reformation that determine the defect states remain poorly understood. Here, we explicitly reveal that the spatial proximity of disintegrated fullerene imposes a crucial impact on the bond reformation and electrocatalytic properties. A counterintuitive hard-template strategy is adopted to enable the space-tuned fullerene restructuring by calcining impregnated C60 not only before but also after the removal of rigid silica spheres (∼300 nm). When confined in the SiO2 nanovoids, the adjacent C60 fragments form sp3 bonding with adverse electron transfer and active site exposure. In contrast, the unrestricted fragments without SiO2 confinement reconnect at the edges to form sp2-hybridized nanosheets while retaining high-density intrinsic defects. The optimized catalyst exhibits robust alkaline oxygen reduction performance with a half-wave potential of 0.82 V via the 4e- pathway. Copper poisoning affirms the intrinsic defects as the authentic active sites. Density functional theory calculations further substantiate that pentagons in the basal plane lead to localized structural distortion and thus exhibit significantly reduced energy barriers for the first O2 dissociation step. Such space-regulated fullerene restructuring is also verified by heating C60 crystals confined in gallium liquid and a quartz tube.

12.
Arch Biochem Biophys ; 745: 109720, 2023 09 01.
Artigo em Inglês | MEDLINE | ID: mdl-37611353

RESUMO

Beauvericin is a world-spread mycotoxin isolated from the traditional Chinese medicine, Bombyx batryticatus (BB), which has been widely used to treat various neoplastic diseases. This study investigated the anti-hepatocellular carcinoma (HCC) activity of beauvericin and its potential mechanism. In this study, H22-bearing mice were intraperitoneally injected with 3, 5, 7 mg/kg of beauvericin once per-week over a three-week period. TUNEL staining determined the extent of tumor apoptosis induced by beauvericin. ELISA kits detected the level of IL-2, Perforin, and TNF-α, IFN-γ level in the serum. H22 hepatoma cells were exposed to beauvericin (5, 10, and 20 µmol/L) to investigate the underlying pathway. CCK-8 assay was used to observe the influence of beauvericin on the growth of H22 cells. Flow cytometry was used to detect the cell apoptosis and ROS level. Western blotting was performed to detect apoptotic and PI3K/AKT pathway protein production. The results showed that beauvericin could remarkably inhibit the growth of HCC in mice, combined with elevated TNF-α and IL-2. In vitro, beauvericin significantly promoted the generation of ROS, up-regulated Bax/Bcl-2 ratio and cleaved caspase-9, cleaved caspase-3 levels, down-regulated p-PI3K/PI3K ratio, p-AKT/AKT ratio, promoted the apoptosis of H22 cells, and inhibited the growth of H22 cells. Remarkably, treatment with PI3K/AKT activator (740Y-P and SC79) could prevent beauvericin-induced H22 cell apoptosis. These findings collectively indicate that beauvericin inhibits HCC growth by inducing apoptosis via the PI3K/AKT pathway.


Assuntos
Carcinoma Hepatocelular , Neoplasias Hepáticas , Animais , Camundongos , Carcinoma Hepatocelular/tratamento farmacológico , Fosfatidilinositol 3-Quinases , Proteínas Proto-Oncogênicas c-akt , Interleucina-2 , Espécies Reativas de Oxigênio , Fator de Necrose Tumoral alfa , Neoplasias Hepáticas/tratamento farmacológico , Apoptose
13.
J Biomed Sci ; 30(1): 29, 2023 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-37101261

RESUMO

Gram-positive (G+) bacterial infection is a great burden to both healthcare and community medical resources. As a result of the increasing prevalence of multidrug-resistant G+ bacteria such as methicillin-resistant Staphylococcus aureus (MRSA), novel antimicrobial agents must urgently be developed for the treatment of infections caused by G+ bacteria. Endolysins are bacteriophage (phage)-encoded enzymes that can specifically hydrolyze the bacterial cell wall and quickly kill bacteria. Bacterial resistance to endolysins is low. Therefore, endolysins are considered promising alternatives for solving the mounting resistance problem. In this review, endolysins derived from phages targeting G+ bacteria were classified based on their structural characteristics. The active mechanisms, efficacy, and advantages of endolysins as antibacterial drug candidates were summarized. Moreover, the remarkable potential of phage endolysins in the treatment of G+ bacterial infections was described. In addition, the safety of endolysins, challenges, and possible solutions were addressed. Notwithstanding the limitations of endolysins, the trends in development indicate that endolysin-based drugs will be approved in the near future. Overall, this review presents crucial information of the current progress involving endolysins as potential therapeutic agents, and it provides a guideline for biomaterial researchers who are devoting themselves to fighting against bacterial infections.


Assuntos
Infecções Bacterianas , Bacteriófagos , Staphylococcus aureus Resistente à Meticilina , Humanos , Infecções Bacterianas/tratamento farmacológico , Bactérias , Bactérias Gram-Positivas , Antibacterianos/farmacologia , Antibacterianos/uso terapêutico
14.
Inorg Chem ; 62(11): 4618-4624, 2023 Mar 20.
Artigo em Inglês | MEDLINE | ID: mdl-36881666

RESUMO

Host-guest structure assembly is significant in the recognition of molecules, and the fullerene-based host-guest structure is a convenient method to determine the structures of fullerenes of which recognition is with many difficulties in experiments. Here, with density functional theory calculations, we designed several crown-shaped pyrrole-based hosts tuned by doping metal atoms (Li, Na, and K) for the effective recognition of C60 with modest interaction between the host and guest. Binding energy calculations showed an enhanced interaction of the concave-convex host-guest system with the doped metal atoms, enabling the selective recognition of C60. The electrostatic interaction between the host and guest was studied by the natural bond order charge analysis, reduced density gradient, and electrostatic potential. Furthermore, the UV-vis-NIR spectra of host-guest structures were simulated to give guidance on the release of the fullerene guest. With much expectation, this work would give a new strategy to design new hosts for effectively recognizing much more fullerene molecules with modest interaction and would be useful for the assembly involving fullerenes.

15.
Inorg Chem ; 62(23): 8993-9004, 2023 Jun 12.
Artigo em Inglês | MEDLINE | ID: mdl-37262348

RESUMO

A new carbonaceous nanohoop, [4]cyclopara-1,2-diphenylethylene ([4]CPDPE, composed by four 1,2-diphenylethylene units linked via the para of the phenyls), is designed together with two rational synthesis paths being proposed. The Saturn-like host-guest systems formed with the [4]CPDPE nanoring and fullerene C60/70 are explored using density functional theory calculations. The results evidence that the geometry mutual matching between [4]CPDPE and C60/70 is perfect, and the [4]CPDPE⊃C60/70 complexes could be formed spontaneously with high binding energies. Thermodynamic calculation results show that it essentially prefers to selectively recognize C70 over its smaller cousin C60. More interestingly, the [4]CPDPE nanoring could present the regular ring cylinder and the saddle shapes via configuration transformation between its all-trans form and all-cis form, so as to theoretically realize the fullerene encapsulation and release under photoirradiation. Furthermore, the 2:1 interaction structure ([4]CPDPE2⊃Dimer-C60) and properties are investigated. Additionally, the ultraviolet-visible (UV-vis) spectra are simulated, and host-guest noncovalent interaction (NCI) regions are investigated based on the electron density and reduced density gradient (RDG), which may be helpful for a deep understanding of the present designed systems in future.

16.
Environ Sci Technol ; 57(25): 9150-9162, 2023 06 27.
Artigo em Inglês | MEDLINE | ID: mdl-37319360

RESUMO

The significant health implications of e-waste toxicants have triggered the global tightening of regulation on informal e-waste recycling sites (ER) but with disparate governance that requires effective monitoring. Taking advantage of the opportunity to implement e-waste control in the Guiyu ER since 2015, we investigated the temporal variations in levels of oxidative DNA damage, 25 volatile organic compound metabolites (VOCs), and 16 metals/metalloids (MeTs) in urine in 918 children between 2016 and 2021 to demonstrate the effectiveness of e-waste control in reducing population exposure risks. The hazard quotients of most MeTs and levels of 8-hydroxy-2'-deoxyguanosine in children decreased significantly during this time, indicating that e-waste control effectively reduces the noncarcinogenic risks of MeT exposure and levels of oxidative DNA damage. Using mVOC-derived indexes as a feature, a bagging-support vector machine algorithm-based machine learning model was constructed to predict the extent of e-waste pollution (EWP). The model exhibited excellent performance with accuracies >97.0% in differentiating between slight and severe EWP. Five simple functions established using mVOC-derived indexes also had high accuracy in predicting the presence of EWP. These models and functions provide a novel human exposure monitoring-based approach for assessing e-waste governance or the presence of EWP in other ERs.


Assuntos
Resíduo Eletrônico , Metaloides , Compostos Orgânicos Voláteis , Criança , Humanos , Metaloides/análise , Estudos Longitudinais , Metais , Reciclagem , China
17.
Phys Chem Chem Phys ; 25(7): 5743-5757, 2023 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-36744403

RESUMO

Developing π electron conjugated groups as covalent bonded bridges between fullerenes in their oligomers is key to optimizing and maximizing functions of the fullerene-based materials. In this work, a series of novel conjugated chain bonded fullerene C60 oligomers (CBFOs) with a well-defined nano-architecture and "grape bunches" shapes are rationally designed and viably constructed based on fullerene-carbenes by means of DFT calculations. The results show that the presently designed CBFOs present a much better electron-accepting ability together with a much lower reorganization energy than the isolated fullerene C60, and characterized as the potential ideal candidate for electron acceptors. The frontier molecular orbital and electron density analysis can well support the results of diabatic electron affinity (EAa) and vertical electron affinity (EAv) calculations. Moreover, these CBFOs exhibit strong absorption in the visible region but no obvious absorption in the ultraviolet region. In addition, the optical properties of the CBFOs and two dimensional structure are also simulated and explored theoretically. We hope that the present study would be helpful for developing covalent-bonded-fullerene based electron trap molecular materials, building blocks of nano-devices and nano-machinery applications.

18.
Hepatobiliary Pancreat Dis Int ; 22(6): 639-644, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37353372

RESUMO

BACKGROUND: Creating a tunnel between the pancreas and splenic vessels followed by pancreatic parenchyma transection ("tunnel-first" strategy) has long been used in spleen-preserving distal pancreatectomy (SPDP) with splenic vessel preservation (Kimura's procedure). However, the operation space is limited in the tunnel, leading to the risks of bleeding and difficulties in suturing. We adopted the pancreatic "parenchyma transection-first" strategy to optimize Kimura's procedure. METHODS: The clinical data of consecutive patients who underwent robotic SPDP with Kimura's procedure between January 2017 and September 2022 at our center were retrieved. The cohort was classified into a "parenchyma transection-first" strategy (P-F) group and a "tunnel-first" strategy (T-F) group and analyzed. RESULTS: A total of 91 patients were enrolled in this cohort, with 49 in the T-F group and 42 in the P-F group. Compared with the T-F group, the P-F group had significantly shorter operative time (146.1 ± 39.2 min vs. 174.9 ± 46.6 min, P < 0.01) and lower estimated blood loss [40.0 (20.0-55.0) mL vs. 50.0 (20.0-100.0) mL, P = 0.03]. Failure of splenic vessel preservation occurred in 10.2% patients in the T-F group and 2.4% in the P-F group (P = 0.14). The grade 3/4 complications were similar between the two groups (P = 0.57). No differences in postoperative pancreatic fistula, abdominal infection or hemorrhage were observed between the two groups. CONCLUSIONS: The pancreatic "parenchyma transection-first" strategy is safe and feasible compared with traditional "tunnel-first strategy" in SPDP with Kimura's procedure.


Assuntos
Laparoscopia , Neoplasias Pancreáticas , Procedimentos Cirúrgicos Robóticos , Humanos , Baço/cirurgia , Pancreatectomia/efeitos adversos , Pancreatectomia/métodos , Neoplasias Pancreáticas/cirurgia , Neoplasias Pancreáticas/complicações , Procedimentos Cirúrgicos Robóticos/efeitos adversos , Resultado do Tratamento , Laparoscopia/efeitos adversos , Complicações Pós-Operatórias/etiologia , Complicações Pós-Operatórias/cirurgia , Artéria Esplênica/cirurgia
19.
Nano Lett ; 22(11): 4544-4551, 2022 06 08.
Artigo em Inglês | MEDLINE | ID: mdl-35604007

RESUMO

Raman-based super multiplexing has attracted great interest in imaging, biological analysis, identity security, and information storage. It still remains a great challenge to synthesize a large number of different Raman-active molecules to fulfill the Raman color palette. Here, we report a facile and systematic strategy to construct continuously multiplexed ultrastrong Raman probes. By precisely incorporating different ratios of 13C isotope into the backbone of poly(deca-4,6-diynedioic acid) (PDDA), we can obtain a library of PDDAs with tunable double-bond Raman frequencies and adjustable intensity ratios of two triple-bond (13C≡13C and 12C≡12C) Raman peaks, while retaining the ultrastrong Raman signals and physicochemical properties of the polymer. We also demonstrate the successful application of 13C-doped PDDAs as security inks to generate a novel 3D matrix barcode system for information encryption and high-density data storage. The isotopically doped PDDA series herein pave a new way to advance Raman-based super multiplexing for diverse applications.


Assuntos
Polímeros , Análise Espectral Raman , Armazenamento e Recuperação da Informação , Análise Espectral Raman/métodos
20.
Cancer Sci ; 113(9): 2986-3001, 2022 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-35534983

RESUMO

Emerging evidence has indicated that long noncoding RNAs (lncRNAs) are potential biomarkers and play crucial roles in cancer development. However, the functions and underlying mechanisms of lncRNA TPT1-AS1 in pancreatic ductal adenocarcinoma (PDAC) remain elusive. RNAseq data of PDAC tissues and normal tissues were analyzed, and lncRNAs which were associated with PDAC prognosis were identified. The clinical relevance of TPT1-AS1 for PDAC patients was explored, and the effects of TPT1-AS1 in PDAC progression were investigated in vitro and in vivo. LncRNA TPT1-AS1 was highly expressed in PDAC, and high TPT1-AS1 levels predicted a poor prognosis. Moreover, functional experiments revealed that TPT1-AS1 promoted pancreatic cancer cell proliferation, migration, invasion, and epithelial-to-mesenchymal transition (EMT) process in vitro and in vivo. Mechanistically, TPT1-AS1 functioned as an endogenous sponge for miR-30a-5p, which increased integrin ß3 (ITGB3) level in pancreatic cancer cells. Conversely, our data revealed that ITGB3 could activate the transcription factor signal transducer and activator of transcription 3 (STAT3), which in turn bound directly to the TPT1-AS1 promoter and affected the expression of TPT1-AS1, thus forming a positive feedback loop with TPT1-AS1. Taken together, our results uncovered a reciprocal loop of TPT1-AS1 and ITGB3 which contributed to pancreatic cancer growth and development, and indicated that TPT1-AS1 might serve as a novel potential diagnostic biomarker and therapeutic target for PDAC patients.


Assuntos
Carcinoma Ductal Pancreático , MicroRNAs , Neoplasias Pancreáticas , RNA Longo não Codificante , Carcinoma Ductal Pancreático/genética , Linhagem Celular Tumoral , Movimento Celular/genética , Proliferação de Células/genética , Retroalimentação , Regulação Neoplásica da Expressão Gênica , Humanos , Integrina beta3/genética , Integrina beta3/metabolismo , MicroRNAs/genética , MicroRNAs/metabolismo , Neoplasias Pancreáticas/genética , Neoplasias Pancreáticas/patologia , RNA Longo não Codificante/genética , RNA Longo não Codificante/metabolismo , Neoplasias Pancreáticas
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