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1.
Chemistry ; : e202402806, 2024 Aug 24.
Artículo en Inglés | MEDLINE | ID: mdl-39180461

RESUMEN

Tunable luminescence-assisted information storage and encryption holds increasing significance in today's society. A promising approach to incorporating the benefits of both organic long persistent luminescent (LPL) materials and rare-earth (RE) luminescence lies in utilizing organic host materials to sensitize RE luminescence, as well as hydrogen-bonded organic framework (HOF) phosphorescence Förster resonance energy transfer to RE compound luminescence. This work introduces a one-pot, in situ pyrolytic condensation method, achieved through high-temperature melting calcination, to synthesize lanthanide ion-doped HOF materials. This method circumvents the drawback of molecular triplet energy annihilation, enabling the creation of organic LPL materials with RE characteristics. The HOF material serves as the host, exhibiting blue phosphorescence and cyan LPL. By fine-tuning the doping amount, the composite material U-Tb-100 achieves green LPL with a luminescent quantum yield of 56.4%, and an LPL duration of approximately 2-3 s, demonstrating tunable persistence. Single-crystal X-ray diffraction, spectral analysis, and theoretical calculation unveil that U-Tb-100 exhibits exceptional quantum yield and long-lived luminescence primarily due to the efficient sensitization of U monomer to RE ions and the PRET process between U and RE complexes. This ingenious strategy not only expands the repertoire of HOF materials but also facilitates the design of multifunctional LPL materials.

2.
BMC Pediatr ; 24(1): 348, 2024 May 20.
Artículo en Inglés | MEDLINE | ID: mdl-38769486

RESUMEN

BACKGROUND: Acute complete gastric volvulus is a rare and life-threatening disease, which is prone to gastric wall ischemia, perforation, and necrosis. If it is not treated by surgery in time, the mortality rate can range from 30 to 50%. Clinical presentations of acute gastric volvulus are atypical and often mimic other abdominal conditions such as gastritis, gastroesophageal reflux, gastric dilation, and pancreatitis. Imaging studies are crucial for diagnosis, with barium meal fluoroscopy being the primary modality for diagnosing gastric volvulus. Cases of acute gastric volvulus diagnosed by ultrasound are rarely reported. CASE PRESENTATION: We reported a rare case of acute gastric volvulus in a 4-year-old Chinese girl who presented with vomiting and abdominal pain. Ultrasound examination revealed the "whirlpool sign" in the cardia region, raising suspicion of gastric volvulus. Diagnosis was confirmed by X-ray barium meal fluoroscopy, which indicated left-sided diaphragmatic hernia and obstruction at the cardia region. Surgical intervention confirmed our suspicion of acute complete gastric volvulus combined with diaphragmatic hernia. CONCLUSION: In this case, we reported an instance of acute complete gastric volvulus. Ultrasound revealed a "whirlpool sign" in the cardia, which is likely to be a key sign for the diagnosis of complete gastric volvulus.


Asunto(s)
Hernias Diafragmáticas Congénitas , Vólvulo Gástrico , Humanos , Vólvulo Gástrico/complicaciones , Vólvulo Gástrico/diagnóstico por imagen , Vólvulo Gástrico/cirugía , Vólvulo Gástrico/diagnóstico , Femenino , Preescolar , Enfermedad Aguda , Hernias Diafragmáticas Congénitas/complicaciones , Hernias Diafragmáticas Congénitas/diagnóstico por imagen , Hernias Diafragmáticas Congénitas/cirugía , Ultrasonografía , Fluoroscopía
3.
Int J Mol Sci ; 25(10)2024 May 09.
Artículo en Inglés | MEDLINE | ID: mdl-38791188

RESUMEN

In our previous studies, a novel cryothermal therapy (CTT) was developed to induce systemic long-term anti-tumor immunity. Natural killer (NK) cells were found to play an important role in CTT-induced long-term immune-mediated tumor control at the late stage after CTT, but the underlying mechanism is unclear. Myeloid-derived suppressor cells (MDSCs) are immature myeloid cells that have potent immunosuppressive effects on T cells and weaken the long-term benefits of immunotherapy. Consequently, overcoming MDSC immunosuppression is essential for maintaining the long-term efficacy of immunotherapy. In this study, we revealed that NK cells considerably diminish MDSC accumulation at the late stage after CTT, boost T cell production, increase T cell activation, and promote MDSC maturation, culminating in Th1-dominant CD4+ T cell differentiation and enhancing NK and CD8+ T cell cytotoxicity. Additionally, NK cells activate ERK signaling in MDSCs through NKG2D-ligand interaction to increase the activity of tumor necrosis factor (TNF)-α converting enzyme (TACE)-cleaved membrane TNF-α. Furthermore, Increased TACE activity releases more soluble TNF-α from MDSCs to promote MDSC maturation. In our studies, we propose a novel mechanism by which NK cells can overcome MDSC-induced immunosuppression and maintain CTT-induced persistent anti-tumor immunity, providing a prospective therapeutic option to improve the performance of cancer immunotherapy.


Asunto(s)
Células Asesinas Naturales , Células Supresoras de Origen Mieloide , Subfamilia K de Receptores Similares a Lectina de Células NK , Factor de Necrosis Tumoral alfa , Células Supresoras de Origen Mieloide/metabolismo , Células Supresoras de Origen Mieloide/inmunología , Células Asesinas Naturales/inmunología , Células Asesinas Naturales/metabolismo , Animales , Subfamilia K de Receptores Similares a Lectina de Células NK/metabolismo , Ratones , Factor de Necrosis Tumoral alfa/metabolismo , Ratones Endogámicos C57BL , Activación de Linfocitos/inmunología , Diferenciación Celular , Ligandos , Proteína ADAM17/metabolismo
4.
Brief Bioinform ; 22(3)2021 05 20.
Artículo en Inglés | MEDLINE | ID: mdl-34020534

RESUMEN

Molecular heterogeneities and complex microenvironments bring great challenges for cancer diagnosis and treatment. Recent advances in single-cell RNA-sequencing (scRNA-seq) technology make it possible to study cancer cell heterogeneities and microenvironments at single-cell transcriptomic level. Here, we develop an R package named scCancer, which focuses on processing and analyzing scRNA-seq data for cancer research. Except basic data processing steps, this package takes several special considerations for cancer-specific features. Firstly, the package introduced comprehensive quality control metrics. Secondly, it used a data-driven machine learning algorithm to accurately identify major cancer microenvironment cell populations. Thirdly, it estimated a malignancy score to classify malignant (cancerous) and non-malignant cells. Then, it analyzed intra-tumor heterogeneities by key cellular phenotypes (such as cell cycle and stemness), gene signatures and cell-cell interactions. Besides, it provided multi-sample data integration analysis with different batch-effect correction strategies. Finally, user-friendly graphic reports were generated for all the analyses. By testing on 56 samples with 433 405 cells in total, we demonstrated its good performance. The package is available at: http://lifeome.net/software/sccancer/.


Asunto(s)
Regulación Neoplásica de la Expresión Génica , Aprendizaje Automático , Neoplasias , ARN Neoplásico , RNA-Seq , Análisis de la Célula Individual , Programas Informáticos , Bases de Datos de Ácidos Nucleicos , Humanos , ARN Neoplásico/biosíntesis , ARN Neoplásico/genética
5.
Int J Mol Sci ; 24(8)2023 Apr 10.
Artículo en Inglés | MEDLINE | ID: mdl-37108179

RESUMEN

Immunosuppression plays a significant role in tumor recurrence and metastasis, ultimately causing poor survival outcomes. Overcoming immunosuppression and stimulating durable antitumor immunity are essential for tumor treatment. In our previous study, a novel cryo-thermal therapy involving liquid nitrogen freezing and radiofrequency heating could reduce the proportion of Myeloid-derived suppressor cells (MDSCs), but the remaining MDSCs produced IL-6 by the NF-κB pathway, resulting in an impaired therapeutic effect. Therefore, here we combined cryo-thermal therapy with anti-IL-6 treatment to target the MDSC-dominant immunosuppressive environment, thereby optimizing the efficacy of cryo-thermal therapy. We found that combinational treatment significantly increased the long-term survival rate of breast cancer-bearing mice. Mechanistic investigation revealed that combination therapy was capable of reducing the proportion of MDSCs in the spleen and blood while promoting their maturation, which resulted in increased Th1-dominant CD4+ T-cell differentiation and enhancement of CD8+ T-mediated tumor killing. In addition, CD4+ Th1 cells promoted mature MDSCs to produce IL-7 through IFN-γ, indirectly contributing to the maintenance of Th1-dominant antitumor immunity in a positive feedback loop. Our work suggests an attractive immunotherapeutic strategy targeting the MDSC-dominant immunosuppressive environment, which would offer exciting opportunities for highly immunosuppressive and unresectable tumors in the clinic.


Asunto(s)
Células Supresoras de Origen Mieloide , Animales , Ratones , Recurrencia Local de Neoplasia , Modelos Animales de Enfermedad , Células TH1 , Terapia Combinada
6.
Angew Chem Int Ed Engl ; 62(52): e202315382, 2023 Dec 21.
Artículo en Inglés | MEDLINE | ID: mdl-37945541

RESUMEN

By synergistically employing four key strategies: (I) introducing tetraphenylethylene groups as the central core unit with aggregation-induced emission (AIE) properties, (II) optimizing the π-conjugated length by extending the building block branches, (III) incorporating flexible groups containing ethylenic bonds, and (IV) applying crystal engineering to attain dense stacking mode and highly twisty conformation, we successfully synthesized a series of hydrogen-bonded organic frameworks (HOFs) exhibiting exceptional one/two-photon excited fluorescence. Notably, when utilizing the fluorescently superior building block L2, HOF-LIFM-7 and HOF-LIFM-8 exhibiting high quantum yields (QY) of 82.1 % and 77.1 %, and ultrahigh two-photon absorption (TPA) cross-sections of 148959.5 GM and 123901.1 GM were achieved. These materials were successfully employed in one and two-photon excited lysosome-targeting cellular imaging. It is believed that this strategy, combining building block optimization and crystal engineering, holds significant potential for guiding the development of outstanding fluorescent HOF materials.

7.
Angew Chem Int Ed Engl ; 62(37): e202309172, 2023 Sep 11.
Artículo en Inglés | MEDLINE | ID: mdl-37488076

RESUMEN

The multiple metastable excited states provided by excited-state intramolecular proton transfer (ESIPT) molecules are beneficial to bring temperature-dependent and color-tunable long persistent luminescence (LPL). Meanwhile, ESIPT molecules are intrinsically suitable to be modulated as D-π-A structure to obtain both one/two-photon excitation and LPL emission simultaneously. Herein, we report the rational design of a dynamic CdII coordination polymer (LIFM-106) from ESIPT ligand to achieve the above goals. By comparing LIFM-106 with the counterparts, we established a temperature-regulated competitive relationship between singlet excimer and triplet LPL emission. The optimization of ligand aggregation mode effectively boost the competitiveness of the latter. In result, LIFM-106 shows outstanding one/two-photon excited LPL performance with wide temperature range (100-380 K) and tunable color (green to red). The multichannel radiation process was further elucidated by transient absorption and theoretical calculations, benefiting for the application in anti-counterfeiting systems.

8.
J Am Chem Soc ; 144(6): 2726-2734, 2022 Feb 16.
Artículo en Inglés | MEDLINE | ID: mdl-35001613

RESUMEN

Excited-state intramolecular proton transfer (ESIPT) molecules demonstrating specific enol-keto tautomerism and the related photoluminescence (PL) switch have wide applications in displaying, sensing, imaging, lasing, etc. However, an ESIPT-attributed coordination polymer showing alternative PL between thermally activated fluorescence (TAF) and long persistent luminescence (LPL) has never been explored. Herein, we report the assembly of a dynamic Cd(II) coordination polymer (LIFM-101) from the ESIPT-type ligand, HPI2C (5-(2-(2-hydroxyphenyl)-4,5-diphenyl-1H-imidazol-1-yl)isophthalic acid). For the first time, TAF and/or color-tuned LPL can be achieved by controlling the temperature under the guidance of ESIPT excited states. Noteworthily, the twisted structure of the HPI2C ligand in LIFM-101 achieves an effective mixture of the higher-energy excited states, leading to ISC (intersystem crossing)/RISC (reverse intersystem crossing) energy transfer between the high-lying keto-triplet state (Tn(K*)) and the first singlet state (S1(K*)). Meanwhile, experimental and theoretical results manifest the occurrence probability and relevance among RISC, ISC, and internal conversion (IC) in this unique ESIPT-attributed coordination polymer, leading to the unprecedented TAF/LPL switching mechanism, and paving the way for the future design and application of advanced optical materials.

9.
Angew Chem Int Ed Engl ; 61(32): e202205556, 2022 Aug 08.
Artículo en Inglés | MEDLINE | ID: mdl-35661372

RESUMEN

Organic LPL (long-persistent luminescence) materials have sparked extensive research interest due to the ultralong-lived triplet states. Although numerous organic LPL materials have been reported, most of the triplet emission was static and monotonous. Therefore, LPL materials with dynamic triplet emission are urgently required. A triamino-s-triazine derivative 1 with dynamic LPL was fabricated. The single-crystal structure shows that the abundant intermolecular interactions and small free volume restrict the molecular motion and avoid the quenchers. Spectral and theoretical calculations upheld the existence of multiple excited states in 1, and the migration of electrons between multiple excited states is very sensitive to external stimuli. By modulating the stimulus, the residence of electrons in different triplet states can be manipulated to achieve RGB LPL. Importantly, blue LPL was achieved by manipulating the anti-Kasha emission. And the red LPL can still be observed at high temperature.

10.
Angew Chem Int Ed Engl ; 61(43): e202211356, 2022 Oct 24.
Artículo en Inglés | MEDLINE | ID: mdl-36055964

RESUMEN

By designing a tetraphenylethylene (TPE)-based AIEgen-ligand with reduced symmetry, we obtained two alkaline-earth metal-based MOFs (LIFM-102 and LIFM-103) with dense packing structures and low porosity as proved by single-crystal X-ray diffraction and CO2 sorption data. Excitingly, the desolvated MOFs with rigid environment and reduced lattice free solvent exhibit high quantum yields (QY, 64.9 % and 79.4 %) and excellent two-photon excited photoluminescence (TPA cross-sections, 2946.6 GM and 2899.0 GM), while maintaining the external-stimuli-responsive properties suitable for anticounterfeit fields. The effect of ligand conformation was validated by comparing the structure and fluorescence properties of the samples before and after desolvation and further verified by theoretical calculations. This work expands the study on TPE-cored materials to symmetry-reduced ligand and might bring forward novel structures and excellent photoluminescent properties in the future.

11.
J Org Chem ; 86(18): 12813-12820, 2021 09 17.
Artículo en Inglés | MEDLINE | ID: mdl-34464127

RESUMEN

Two novel derivatives of 2-methyl-1-(2,3,4,6-tetrahydroxyphenyl)propan-1-one and (S)-2-methyl-1-(2,3,4,6-tetrahydroxyphenyl)butan-1-one (1 and 2), four novel six-membered lactone phenols (3-6), and a nor-ursane type triterpenoid (7) named Achroacid, were isolated from the aerial part of Achyrocline satureioides. The absolute configurations of 1-7 are presented by spectroscopic data and X-ray crystallographic analysis. A DP4plus evaluation was applied to determine the final stereochemistry for 1 and 2. The biosynthesis pathway of 1 and 2 was proposed. 1 has potential on anti-Gram-negative bacteria. Both 1 and 2 exhibited a significant impact on anti-H1299 cells. Compounds 3-7 showed moderate cancer cell lethality and significant anti-inflammatory activities.


Asunto(s)
Achyrocline , Triterpenos , Lactonas , Polifenoles , Esqueleto , Triterpenos/farmacología
12.
BMC Musculoskelet Disord ; 22(1): 316, 2021 Mar 30.
Artículo en Inglés | MEDLINE | ID: mdl-33785016

RESUMEN

BACKGROUND: Postoperative residual knee pain after total knee arthroplasty (TKA) is a significant factor that contributes to patient dissatisfaction. Patients with preoperative central sensitization (CS) may be more susceptible to unexplained chronic pain after TKA, and duloxetine has been reported to be effective in post-TKA pain control in patients with CS. However, there remains limited evidence to support this off-label use in routine clinical practice. Hence, we designed this randomized, placebo-controlled, triple-blind clinical trial to evaluate the effects of preoperative screening and targeted duloxetine treatment of CS on postoperative residual pain compared with the care-as-usual control group. METHODS: This randomized controlled trial includes patients with knee osteoarthritis on a waiting list for primary unilateral TKA. Patients with preoperative CS will be randomly allocated to the perioperative duloxetine treatment group (duloxetine group) or the care-as-usual control group (placebo group). Patients in the duloxetine group will receive a half-dose of preemptive duloxetine (30 mg/day) for a week before surgery and a full-dose of duloxetine (60 mg/day) for six weeks after surgery. The primary outcome is the intensity of residual pain at six months after TKA, including the visual analogue scale, 11-point numeric rating scale, the sensory dimension of the brief pain inventory, and the pain subscale of the Knee injury and Osteoarthritis Outcome Score. The secondary outcome measures will include the pain and function related outcomes. All of the patients will be followed up at one, three, and six months after surgery. All adverse events will be recorded and immediately reported to the primary investigator and ethics committee to decide if the patient needs to drop out from the trial. DISCUSSION: This clinical trial will convey the latest evidence of the efficacy and safety of the application of duloxetine in postoperative pain control in CS patients who are scheduled for TKA. The study results will be disseminated at national and international conferences and published in peer-reviewed journals. TRIAL REGISTRATION: Chinese Clinical Trial Registry ( http://www.chictr.org.cn ) registration number: ChiCTR2000031674 . Registered 07 April 2020.


Asunto(s)
Artroplastia de Reemplazo de Rodilla , Osteoartritis de la Rodilla , Artroplastia de Reemplazo de Rodilla/efectos adversos , Clorhidrato de Duloxetina/efectos adversos , Humanos , Osteoartritis de la Rodilla/tratamiento farmacológico , Osteoartritis de la Rodilla/cirugía , Dolor Postoperatorio/diagnóstico , Dolor Postoperatorio/tratamiento farmacológico , Dolor Postoperatorio/etiología , Ensayos Clínicos Controlados Aleatorios como Asunto , Resultado del Tratamiento
13.
Int J Mol Sci ; 22(13)2021 Jun 29.
Artículo en Inglés | MEDLINE | ID: mdl-34209797

RESUMEN

Macrophages play critical roles in both innate and adaptive immunity and are known for their high plasticity in response to various external signals. Macrophages are involved in regulating systematic iron homeostasis and they sequester iron by phagocytotic activity, which triggers M1 macrophage polarization and typically exerts antitumor effects. We previously developed a novel cryo-thermal therapy that can induce the mass release of tumor antigens and damage-associated molecular patterns (DAMPs), promoting M1 macrophage polarization. However, that study did not examine whether iron released after cryo-thermal therapy induced M1 macrophage polarization; this question still needed to be addressed. We hypothesized that cryo-thermal therapy would cause the release of a large quantity of iron to augment M1 macrophage polarization due to the disruption of tumor cells and blood vessels, which would further enhance antitumor immunity. In this study, we investigated iron released in primary tumors, the level of iron in splenic macrophages after cryo-thermal therapy and the effect of iron on macrophage polarization and CD4+ T cell differentiation in metastatic 4T1 murine mammary carcinoma. We found that a large amount of iron was released after cryo-thermal therapy and could be taken up by splenic macrophages, which further promoted M1 macrophage polarization by inhibiting ERK phosphorylation. Moreover, iron promoted DC maturation, which was possibly mediated by iron-induced M1 macrophages. In addition, iron-induced M1 macrophages and mature DCs promoted the differentiation of CD4+ T cells into the CD4 cytolytic T lymphocytes (CTL) subset and inhibited differentiation into Th2 and Th17 cells. This study explains the role of iron in cryo-thermal therapy-induced antitumor immunity from a new perspective.


Asunto(s)
Linfocitos T CD4-Positivos/efectos de los fármacos , Crioterapia/efectos adversos , Hierro/metabolismo , Hierro/farmacología , Activación de Macrófagos/efectos de los fármacos , Linfocitos T Citotóxicos/efectos de los fármacos , Animales , Linfocitos T CD4-Positivos/fisiología , Diferenciación Celular/efectos de los fármacos , Diferenciación Celular/inmunología , Polaridad Celular/efectos de los fármacos , Células Cultivadas , Femenino , Quelantes del Hierro/farmacología , Activación de Linfocitos/efectos de los fármacos , Activación de Macrófagos/fisiología , Macrófagos/efectos de los fármacos , Macrófagos/fisiología , Ratones , Ratones Endogámicos BALB C , Células RAW 264.7 , Linfocitos T Citotóxicos/fisiología
14.
Int J Mol Sci ; 22(18)2021 Sep 15.
Artículo en Inglés | MEDLINE | ID: mdl-34576115

RESUMEN

Immunotherapy has emerged as a therapeutic pillar in tumor treatment, but only a minority of patients get benefit. Overcoming the limitations of immunosuppressive environment is effective for immunotherapy. Moreover, host T cell activation and longevity within tumor are required for the long-term efficacy. In our previous study, a novel cryo-thermal therapy was developed to improve long-term survival in B16F10 melanoma and s.q. 4T1 breast cancer mouse models. We determined that cryo-thermal therapy induced Th1-dominant CD4+ T cell differentiation and the downregulation of Tregs in B16F10 model, contributing to tumor-specific and long-lasting immune protection. However, whether cryo-thermal therapy can affect the differentiation and function of T cells in a s.q. 4T1 model remains unknown. In this study, we also found that cryo-thermal therapy induced Th1-dominant differentiation of CD4+ T cells and the downregulation of effector Tregs. In particular, cryo-thermal therapy drove the fragility of Tregs and impaired their function. Furthermore, we discovered the downregulated level of serum tumor necrosis factor-α at the late stage after cryo-thermal therapy which played an important role in driving Treg fragility. Our findings revealed that cryo-thermal therapy could reprogram the suppressive environment and induce strong and durable antitumor immunity, which facilitate the development of combination strategies in immunotherapy.


Asunto(s)
Crioterapia , Regulación hacia Abajo , Neoplasias/inmunología , Neoplasias/terapia , Linfocitos T Reguladores/inmunología , Factor de Necrosis Tumoral alfa/metabolismo , Animales , Diferenciación Celular , Línea Celular Tumoral , Femenino , Terapia de Inmunosupresión , Ratones , Ratones Endogámicos BALB C , Metástasis de la Neoplasia , Pruebas de Neutralización , Fenotipo , Ablación por Radiofrecuencia , Factor de Necrosis Tumoral alfa/sangre
15.
Int J Mol Sci ; 22(20)2021 Oct 13.
Artículo en Inglés | MEDLINE | ID: mdl-34681680

RESUMEN

Effective cancer therapies should reshape immunosuppression and trigger antitumor immunity. Previously, we developed a novel cryo-thermal therapy through applying local rapid cooling followed by rapid heating of tumor tissue. It could not only ablate local tumors, but also, subsequently, induce systemic long-term antitumor immunity. Hyperthermia can induce the release of extracellular vesicles (EVs) to stimulate antitumor immunity. We examine whether EVs are released after cryo-thermal therapy and whether they could improve the efficacy of cryo-thermal therapy in the 4T1 model. In this study, serum extracellular vesicles (sEVs) are isolated and characterized 3 h after cryo-thermal therapy of subcutaneous tumors. sEV phagocytosis is observed in vitro and in vivo by using laser confocal microscopy and flow cytometry. After cryo-thermal therapy, sEVs are administered to mice via the tail vein, and changes in immune cells are investigated by using flow cytometry. After cryo-thermal therapy, a large number of sEVs are released to the periphery carrying danger signals and tumor antigens, and these sEVs could be phagocytosed by peripheral blood monocytes and differentiated macrophages. After cryo-thermal therapy, supplementation with sEVs released after treatment promotes the differentiation of myeloid-derived suppressor cells (MDSCs), monocytes into macrophages and CD4+ T cells into the Th1 subtype, as well as prolonging the long-term survival of the 4T1 subcutaneous tumor-bearing mice. sEVs released after cryo-thermal tumor treatment could clinically serve as an adjuvant in subsequent cryo-thermal therapy to improve the therapeutic effects on malignant tumors.


Asunto(s)
Crioterapia , Vesículas Extracelulares , Neoplasias/terapia , Animales , Antígenos de Neoplasias , Linfocitos T CD4-Positivos/inmunología , Línea Celular Tumoral , Femenino , Macrófagos/inmunología , Ratones , Monocitos/inmunología , Neoplasias/inmunología , Células RAW 264.7
16.
J Am Chem Soc ; 142(39): 16661-16667, 2020 09 30.
Artículo en Inglés | MEDLINE | ID: mdl-32881485

RESUMEN

A two-ligand system composed of the predesigned multivalent and complementary terpyridine-based ligands was exploited to construct heteroleptic metallo-supramolecules and to investigate the self-assembly mechanism. Molecular stellation of the trimeric hexagon [Cd6L23] gave rise to the exclusive self-assembly of the star hexagon [Cd18L16L33] through complementary ligand pairing between the ditopic and octatopic tectons. To understand how the intermolecular heteroleptic complexation influenced the self-assembly pathway, the star hexagon was truncated into two triangular fragments: [Cd12L13L43] and [Cd12L13L53]. In the self-assembly of [Cd12L13L43], the conformational movements of hexatopic ligand L4 could be regulated by L1 to promote the subsequent coordination event, which was the key step to the successful multicomponent self-assembly. In contrast, the formation of [Cd12L13L53] was hampered by the geometrically mismatched intermediates.

17.
J Am Chem Soc ; 142(15): 7134-7144, 2020 04 15.
Artículo en Inglés | MEDLINE | ID: mdl-32150683

RESUMEN

Tetrafunctionalized calix[4]resorcinarene cavitands commonly serve as supramolecular scaffolds for construction of coordination-driven self-assembled capsules. However, due to the calix-like shape, the structural diversity of assemblies is mostly restricted to dimeric and hexameric capsules. Previously, we reported a spontaneous heteroleptic complexation strategy based on a pair of self-recognizable terpyridine-based ligands and CdII ions. Building on this complementary ligand pairing system, herein three types of nanocapsules, including a dimeric capsule, a Sierpinski triangular prism, and a cubic star, could be readily obtained through dynamic complexation reactions between a tetratopic cavitand-based ligand and various multitopic counterparts in the presence of CdII ions. The dimeric capsular assemblies display the spacer-length-dependent self-sorting behavior in a four-component system. Moreover, the precise multicomponent self-assembly of a Sierpinski triangular prism and a cubic star possessing three and six cavitand-based motifs, respectively, demonstrates that such self-assembly methodology is able to efficiently enhance architectural complexity for calix[4]resorcinarene-containing metallo-supramolecules.

18.
J Am Chem Soc ; 142(10): 4663-4670, 2020 Mar 11.
Artículo en Inglés | MEDLINE | ID: mdl-32033517

RESUMEN

Gigantic coordination molecules assembled from a large number of metal ions and organic ligands are structurally and functionally challenging to characterize. Here we show that a heterometallic cluster [Ni36Gd102(OH)132(mmt)18(dmpa)18(H2dmpa)24(CH3COO)84(SO4)18(NO3)18(H2O)30]·Br6(NO3)6·(H2O)x·(CH3OH)y, (1, x ≈ 130, y ≈ 60), shaped like a "Star of David", can be synthesized using a "mixed-ligand" and "sulfate-template" strategy. In terms of metal nuclearity number, 1 is the second largest 3d-4f cluster to date. In the solid state, 1 is porous after removing the lattice guests. The N2 adsoption experiment reveals that the BET and Langmuir surface areas are 299.8 and 412.0 cm2 g-1, respectively. CO2 adsorption at 298 K gives the amount of 45 cm3 g-1 for 1. More importantly, 1 is soluble in common organic solvents and exhibits high solution stability revealed by high resolution MALDI-TOF mass spectroscopy, small-angle X-ray scattering (SAXS), and low-dose transmission electron microscopy. The solubility and the potential open metal sites owing to the labile coordinating components prompted us to investigate the photocatalytic properties of 1, which displays high selectivity and efficiency for reduction of CO2 to CO with turnover number and turnover frequency of 29700 and 1.2 s-1, respectively. These values are higher than most catalysts working under the same conditions, presumably due to the strong Ni-CO2 binding effect. In addition, the large percentage of Gd(III) in 1 leads to a large magnetic entropy change (41.3 J·kg-1·K-1) at 2.0 K for ΔH = 7 T.

19.
Inorg Chem ; 59(9): 6078-6086, 2020 May 04.
Artículo en Inglés | MEDLINE | ID: mdl-32310645

RESUMEN

The fabrication of highly efficient and sustainable electrocatalysts used for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is exceedingly challenging and warranted for overall water splitting. In this work, we successfully synthesized a series of metal-organic frameworks (MOFs), namely, as Fe2M-MOF (M = Fe, Co, Ni, Zn, Mn; H4L = 3,3,5,5'-azoxybenzenetetracarboxylic acid) under a simple and mild condition, in which the Fe3 cluster as a basic building unit was replaced by the second kind of metal center; at the same time, a redox-active organic linker was adopted. The Fe2M-MOF system as a multifunctional catalyst realizes great improvement of the OER and HER performances. Among of them, the Fe2Co-MOF catalyst exhibits an extremely low overpotential of 339 mV at a current density of 10 mA cm-2 and a very small Tafel slope of 36.2 mV dec-1 in an alkaline electrolyte for OER. This result has far exceeded the commercial catalyst IrO2. Meanwhile, Fe2Zn-MOF manifests excellent HER activity with a small overpotential of 221 mV at 10 mA cm-2 and a low Tafel slope of 174 mV dec-1. In addition, the good long-term stability for these catalysts can be evaluated under working conditions. Systematic investigations are used to explain the enhanced electrocatalytic mechanism. In conclusion, we provide a simple and effective strategy for the preparation of multifunctional catalysts for energy conversion applications based on a pristine MOF material with redox-active metal centers and organic linkers.

20.
Inorg Chem ; 59(9): 6640-6645, 2020 May 04.
Artículo en Inglés | MEDLINE | ID: mdl-32286799

RESUMEN

A metal-organic supramolecular nanobelt was synthesized by quantitative self-assembling terpyridine-functionized tetraphenylethylene (TPE) and Cd2+, which only showed a weak emission both in solution or aggregated state. Nevertheless, nanobelt complex could be transferred to a fluorescence turn-on sensor to S2- by taking advantage of the structural transformation from nanobelt to its fluorescent ligand.

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