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1.
Proc Natl Acad Sci U S A ; 119(22): e2202449119, 2022 05 31.
Artículo en Inglés | MEDLINE | ID: mdl-35622888

RESUMEN

Organodisulfides (RSSR) are a class of promising active materials for redox flow batteries (RFBs). However, their sluggish kinetics and poor cyclic stability remain a formidable challenge. Here, we propose carbon disulfide (CS2) as a unique redox mediator involving reversible C-S bond formation/breakage to facilitate the reduction reaction of organodisulfides in RFBs. In the discharge of RSSR, CS2 interacts with the negatively charged RSSR-• to promote cleavage of the S-S bond by reducing about one-third of the energy barrier, forming RSCS2Li. In the recharge, CS2 is unbonded from RSCS2Li while RSSR is regenerated. Meanwhile, the redox mediator can also be inserted into the molecular structure of RSSR to form RSCS2SR/RSCS2CS2SR, and these new active materials with lower energy barriers can further accelerate the reaction kinetics of RSSR. With CS2, phenyl disulfide exhibits an exceptional rate capability and cyclability of 500 cycles. An average energy efficiency of >90% is achieved. This strategy provides a unique redox-mediating pathway involving C-S bond formation/breakage with the active species, which is different from those used in lithium-oxygen or other batteries.

2.
Inorg Chem ; 63(5): 2776-2786, 2024 Feb 05.
Artículo en Inglés | MEDLINE | ID: mdl-38266170

RESUMEN

Developing efficient heterogeneous catalysts for chemical fixation of CO2 to produce high-value-added chemicals under mild conditions is highly desired but still challenging. Herein, we first reported an approach to prepare a novel catalyst (Ag@NCNFs), featuring Ag nanoparticles (NPs) embedded within porous nitrogen-doped carbon nanofibers (NCNFs), via growing a Ag metal-organic framework on one-dimensional electrospun nanofibers followed by pyrolysis. Benefiting from the abundant nitrogen species and porous structure, Ag NPs is well dispersed in the obtained Ag@NCNFs. Catalytic studies indicated that Ag@NCNFs exhibited excellent catalytic activity for the three-component coupling reaction of CO2, secondary amines, and propargylic alcohols to generate ß-oxopropylcarbamates under mild conditions with a turnover number (TON) of 16.2, and it can be recycled and reused at least 5 times without an obvious decline in catalytic activity. The reaction mechanism was clearly clarified by FTIR, NMR, 13C isotope labeling, control experiments, and density functional theory calculations. The results suggest that Ag@NCNFs and 1,8-diazabicyclo[5.4.0]undec-7-ene can synergistically activate propargylic alcohol to react with CO2, and then the generated α-alkylidene cyclic carbonate was invaded by secondary amine to produce ß-oxopropylcarbamate. Importantly, to the best of our knowledge, this is the first experimental and theoretical investigation on this reaction.

3.
J Biochem Mol Toxicol ; 38(4): e23676, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38561971

RESUMEN

Although the treatment of ovarian cancer has made great progress, there are still many patients who are not timely detected and given targeted therapy due to unknown pathogenesis. Recent studies have found that hsa_circ_0015326 is upregulated in ovarian cancer and is involved in the proliferation, invasion, and migration of ovarian cancer cells. However, whether hsa_circ_0015326 can be used as a new target of ovarian cancer needs further investigation. Therefore, the effect of hsa_circ_0015326 on epithelial ovarian cancer was investigated in this study. At first, si-hsa_circ_0015326 lentivirus was transfected into epithelial ovarian cancer cells. Then real-time fluorescence quantitative PCR (qRT-PCR) was used to detect hsa_circ_0015326 level. The proliferation of ovarian cancer cells was detected by CCK-8 assay. The horizontal and vertical migration abilities of the cells were detected by wound-healing assay and Transwell assay, respectively. Transwell assay was also used to determine the invasion rate. As for the apoptosis rate, it was assessed by flow cytometry. As a result, the expression level of hsa_circ_0015326 in A2780 and SKOV3 was found to be higher than that in IOSE-80. However, after transfecting si-hsa_circ_0015326 and si-NC into the cells, the proliferation, migration, and invasion abilities of A2780 and SKOV3 cells in the si-hsa_circ_0015326 group were significantly reduced in comparison to those in the si-NC and mock groups, while their apoptosis rates were elevated. Collectively, silencing hsa_circ_0015326 bears the capability of inhibiting the proliferation, migration, and invasion of ovarian cancer cells while increasing apoptosis rate. It can be concluded that hsa_circ_0015326 promotes the malignant biological activities of epithelial ovarian cancer cells.


Asunto(s)
MicroARNs , Neoplasias Ováricas , Humanos , Femenino , ARN/metabolismo , Carcinoma Epitelial de Ovario/genética , ARN Circular/genética , ARN Circular/metabolismo , Línea Celular Tumoral , Neoplasias Ováricas/genética , Neoplasias Ováricas/patología , Proliferación Celular , Apoptosis , MicroARNs/metabolismo , Movimiento Celular
4.
Sensors (Basel) ; 24(2)2024 Jan 09.
Artículo en Inglés | MEDLINE | ID: mdl-38257490

RESUMEN

Occlusion in facial photos poses a significant challenge for machine detection and recognition. Consequently, occluded face recognition for camera-captured images has emerged as a prominent and widely discussed topic in computer vision. The present standard face recognition methods have achieved remarkable performance in unoccluded face recognition but performed poorly when directly applied to occluded face datasets. The main reason lies in the absence of identity cues caused by occlusions. Therefore, a direct idea of recovering the occluded areas through an inpainting model has been proposed. However, existing inpainting models based on an encoder-decoder structure are limited in preserving inherent identity information. To solve the problem, we propose ID-Inpainter, an identity-guided face inpainting model, which preserves the identity information to the greatest extent through a more accurate identity sampling strategy and a GAN-like fusing network. We conduct recognition experiments on the occluded face photographs from the LFW, CFP-FP, and AgeDB-30 datasets, and the results indicate that our method achieves state-of-the-art performance in identity-preserving inpainting, and dramatically improves the accuracy of normal recognizers in occluded face recognition.


Asunto(s)
Reconocimiento Facial , Señales (Psicología) , Reconocimiento en Psicología
5.
Pak J Med Sci ; 40(6): 1135-1139, 2024 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-38952522

RESUMEN

Objective: To compare the uniportal and multiportal video-assisted thoracoscopic surgery (VATS) in patients with non-small-cell lung cancer (NSCLC). Methods: Medical records of 128 patients with NSCLC who underwent surgical treatment in the First School of Clinical Medicine, Southern Medical University from August 2020 to February 2022 were retrospectively analyzed. There were 60 patients who underwent uniportal VATS (UVATS group) and 68 patients underwent multiportal VATS (MVATS group). The relevant indexes, complications, postoperative pain levels and quality of life, recurrence, metastases and survival between the two groups were compared. Results: UVATS was associated with longer operation time and higher intraoperative blood loss compared to MVATS (P<0.05). The postoperative drainage volume, and the visual analogue scale (VAS) scores at 24 and 72 hours were lower in the UVATS group compared to the MVATS group, while the chest tube retention time and hospitalization time were shorter than those in the MVATS group (P<0.05). The quality of life at six months after surgery in the UVATS group was significantly higher than that in the MVATS group (P<0.05). Conclusions: UVATS and MVATS have similar outcomes in patients with NSCLC. Although UVATS surgery takes longer and is associated with more interoperative bleeding, it can reduce postoperative pain, shorten postoperative recovery time, and help further improve the quality of life of patients after surgery.

6.
Inorg Chem ; 62(37): 14902-14911, 2023 Sep 18.
Artículo en Inglés | MEDLINE | ID: mdl-37651103

RESUMEN

A series of bifunctional Ln(III)-based coordination polymers (CPs) {Ln(L)(DMA)2(NO3)}n [Ln(III) = Eu (1), Gd (2), and Dy (3); organic ligand H2L = 2,2'-(1,3,5,7-tetrahydroxyoctahydro-4,8-ethanopyrrolo[3,4-f]isoindole-2,6(1H,3H)-diyl)diacetic acid)] have been successfully synthesized. CPs 1-3 are isostructural and constructed from the dimeric Ln2 unit in which two adjacent LnIII ions are bridged by two µ3-carboxyl oxygens, and the Ln2 dimeric unit is connected by two NO3- ions, four DMA molecules, and four completely protonated L2- ligands forming a 2D layer structure. The magnetic research reveals that CP 2 shows a significant cryogenic magnetocaloric effect (-ΔSm = 22.9 J kg-1 K-1; T = 2.0 K and ΔH = 7.0 T), whereas CP 3 exhibits slow magnetic relaxation property under Hdc = 0 Oe field. Additionally, the luminescence explorations revealed that CP 1 can act as a recyclable luminescent probe for pollutant acetylacetone among various small organic solvent molecules, and the corresponding detection limit is 10-7 mol/L. More importantly, CP 1 also exhibits good catalytic performance in the cycloaddition reaction of CO2 and epoxides or cyanamides under mild conditions. As far as we know, CP 1 represents the first bifunctional lanthanide homogeneous catalyst that can efficiently catalyze the reaction of cyanamides/epoxides with CO2 simultaneously.

7.
Nano Lett ; 22(15): 6366-6374, 2022 Aug 10.
Artículo en Inglés | MEDLINE | ID: mdl-35904355

RESUMEN

Although single-atom catalysts (SACs) have been largely explored in lithium-sulfur (Li-S) batteries, the commonly reported nonpolar transition metal-N4 coordinations only demonstrate inferior adsorption and catalytic activity toward shuttled lithium polysulfides (LiPSs). Herein, single Fe atoms with asymmetric coordination configurations of Fe-N3C2-C were precisely designed and synthesized as efficient immobilizer and catalyst for LiPSs. The experimental and theoretical results elucidate that the asymmetrically coordinated Fe-N3C2-C moieties not only enhance the LiPSs anchoring capability by the formation of extra π-bonds originating from S p orbital and Fe dx2-y2/dxy orbital hybridization but also boost the redox kinetics of LiPSs with reduced Li2S precipitation/decomposition barrier, leading to suppressed shuttle effect. Consequently, the Li-S batteries assembled with Fe-N3C2-C exhibit high areal capacity and cycling stability even under high sulfur loading and lean electrolyte conditions. This work highlights the important role of coordination symmetry of SACs for promoting the practical application of Li-S batteries.

8.
J Am Chem Soc ; 144(41): 18918-18926, 2022 10 19.
Artículo en Inglés | MEDLINE | ID: mdl-36194783

RESUMEN

Organosulfides are promising cathodes for lithium batteries but often suffer from sluggish kinetics and low cycle stability. Herein, we report an electron-deficient organosulfide (ED-OS), which is formed via electrochemical oxidation of thiuram monosulfide, a low-cost sustainable material. The ED structure of (dimethylcarbamothioyl)thio can stretch the electron cloud of the adjacent C═S bond forming an S radical and lead to the cleavage of the S-C bond on the other side forming another S radical. The two (dimethylcarbamothioyl)thio radicals can form S-S bonds individually with low energy barriers, which thus are easy to break and could accommodate lithium ions with ultrafast reaction kinetics. It exhibits an ultralong cyclability of over 8000 cycles with a low capacity-fade rate of 0.0038% per cycle at a high rate of 10C in a lithium cell. In addition, we demonstrate that the same electrochemical oxidation can be applied to other thiuram compounds. This work provides new opportunities in developing ultrahigh-redox-activity organic electrode materials which can be started as needed.


Asunto(s)
Litio , Tiram , Suministros de Energía Eléctrica , Oxidación-Reducción , Iones
9.
Inorg Chem ; 61(38): 15098-15107, 2022 Sep 26.
Artículo en Inglés | MEDLINE | ID: mdl-36094135

RESUMEN

A series of heterometallic tetranuclear clusters, Ln2Ni2(NO3)4L4(µ3-OCH3)2·2(CH3CN) (Ln = Gd(1), Tb(2), Dy(3), Ho(4), Er(5); HL = methyl 3-methoxysalicylate), were synthesized solvothermally. The intramolecular synergistic effect of two metal centers of Ln(III) and Ni(II) and the exposed multimetallic sites serving as Lewis acid activators greatly increase the efficiency of the CO2 conversion, and the yield for cluster 3 can be achieved at 96% at atmospheric pressure and low temperature. In particular, the self-assembly multimetal center with polydentate ligand shows good generality and enhanced recyclability. The design of such 3d-4f heterometallic clusters provides an effective strategy for the conversion of CO2 under greener conditions. Meanwhile, magnetic investigations indicate that cluster 1 is a good candidate for magnetic refrigerant materials with a relatively large magnetocaloric effect (MCE) (-ΔSm = 28.5 J kg-1 K-1 at 3.0 K and 7.0 T), and cluster 3 shows single-molecular magnet behavior under zero dc field. Heterometallic clusters with special magnetic properties and good catalytic behavior for the conversion of CO2 are rare. Thus, they are potential bifunctional materials applied in practice.

10.
Sensors (Basel) ; 22(16)2022 Aug 15.
Artículo en Inglés | MEDLINE | ID: mdl-36015851

RESUMEN

An event camera is a novel bio-inspired sensor that effectively compensates for the shortcomings of current frame cameras, which include high latency, low dynamic range, motion blur, etc. Rather than capturing images at a fixed frame rate, an event camera produces an asynchronous signal by measuring the brightness change of each pixel. Consequently, an appropriate algorithm framework that can handle the unique data types of event-based vision is required. In this paper, we propose a dynamic object tracking framework using an event camera to achieve long-term stable tracking of event objects. One of the key novel features of our approach is to adopt an adaptive strategy that adjusts the spatiotemporal domain of event data. To achieve this, we reconstruct event images from high-speed asynchronous streaming data via online learning. Additionally, we apply the Siamese network to extract features from event data. In contrast to earlier models that only extract hand-crafted features, our method provides powerful feature description and a more flexible reconstruction strategy for event data. We assess our algorithm in three challenging scenarios: 6-DoF (six degrees of freedom), translation, and rotation. Unlike fixed cameras in traditional object tracking tasks, all three tracking scenarios involve the simultaneous violent rotation and shaking of both the camera and objects. Results from extensive experiments suggest that our proposed approach achieves superior accuracy and robustness compared to other state-of-the-art methods. Without reducing time efficiency, our novel method exhibits a 30% increase in accuracy over other recent models. Furthermore, results indicate that event cameras are capable of robust object tracking, which is a task that conventional cameras cannot adequately perform, especially for super-fast motion tracking and challenging lighting situations.


Asunto(s)
Algoritmos , Procesamiento de Imagen Asistido por Computador , Procesamiento de Imagen Asistido por Computador/métodos , Iluminación , Movimiento (Física) , Visión Ocular
11.
Inorg Chem ; 60(12): 9122-9131, 2021 Jun 21.
Artículo en Inglés | MEDLINE | ID: mdl-34061517

RESUMEN

A new porous copper-organic framework assembled from 12-nuclear [Cu12] nanocages {[Cu2(L4-)(H2O)2]·4DMA·2H2O}n (1) (H4L = 5,5'-(butane-1,4-diyl)-bis(oxy)-diisophthalic acid) was successfully prepared and structurally characterized. Compound 1 feathering of a 3D framework with two types of 1D nanotubular channels and a large specific surface area can effectively enrich various harmful dyes. Additionally, due to the carbon dioxide (CO2) interactions with open Cu(II) sites and the electron-rich ether oxygen atoms of ligand in 1, it exhibits a highly selective CO2 uptake. Interestingly, 1 can effectively catalyze the cycloaddition reaction of CO2 with various epoxides under mild conditions, which is ascribed to the Lewis acid Cu(II) sites in the framework of 1. Importantly, 1 acting as a heterogeneous catalyst can be recycled at least 10 times without an obvious loss of catalytic activity, and the CO2 cycloaddition mechanism was further uncovered by density functional theory (DFT) calculations. This study can greatly enrich the MOF catalysts system of CO2 conversion and also provide a valuable guidance for the design of efficient MOFs catalysts.

12.
Ecotoxicol Environ Saf ; 217: 112206, 2021 Jul 01.
Artículo en Inglés | MEDLINE | ID: mdl-33866286

RESUMEN

1,4-Dioxane (dioxane), an emerging groundwater contaminant, is frequently detected in landfill leachates with its structural analog, tetrahydrofuran (THF). Along with undesirable leakage of landfill leachates, dioxane and THF inevitably percolate into groundwater leading to a broader region of contamination. Cometabolic bioremediation is an effective approach to manage commingled THF and dioxane pollution. In this study, a newly isolated bacterium Arthrobacter sp. WN18 is able to co-oxidize dioxane with THF as the primary substrate. Meanwhile, the THF-induced thmADBC gene cluster was responsible for the dioxane degradation rate indicating THF monooxygenase is the essential enzyme that initializing α-hydroxylation of THF and dioxane. Further, γ-butyrolactone and HEAA were characterized as the key metabolites of THF and dioxane, respectively. In addition, WN18 can tolerate the inhibition of trichloroethylene (5.0 mg/L) as a representative of co-existing leachate constituent, and sustain its activity at various pH (5-11), temperatures (15-42 °C), and salinities (up to 4%, as NaCl wt). Like other Arthrobacter species, WN18 also exhibited the capability of fixing nitrogen. All this evidence indicates the feasibility and advantage of WN18 as a thmADBC-catalyzed inoculator to bioremediate co-contamination of THF and dioxane.


Asunto(s)
Arthrobacter/metabolismo , Biodegradación Ambiental , Dioxanos/metabolismo , Furanos/metabolismo , Proteínas Bacterianas , Agua Subterránea , Oxigenasas de Función Mixta , Familia de Multigenes , Oxidación-Reducción , Tricloroetileno , Contaminantes Químicos del Agua
13.
Inorg Chem ; 59(20): 15111-15119, 2020 Oct 19.
Artículo en Inglés | MEDLINE | ID: mdl-32997940

RESUMEN

Two structurally similar metal-organic frameworks (MOFs) [Dy2Cu4I3(IN)7(DMF)2]·DMF (1) and [Dy2Cu4I3(IN)7(DMA)2]·DMA (2) (HIN = isonicotinic acid) feathering different coordinated solvent molecules were successfully isolated by tuning the types of solvents in the reaction system. Structural tests indicate that 1 and 2 are both built from 1D Dy(III) chains and copper iodide clusters [Cu4I3], generating into three-dimensional frameworks with an open 1D channel along the a axis. 1 and 2 display extensive and excellent solvent stability. Magnetic studies of 1 and 2 indicate that they exhibit interesting solvent-dependent magnetization dynamics. Importantly, 1 and 2 can act as highly effective catalysts for the carboxylic cyclization of propargyl alcohols with carbon dioxide (CO2) under ambient operating conditions. Additionally, the substrate scope was further explored over compound 1 based on the optimal conditions, and it exhibits efficient cyclic carboxylation of various terminal propargylic alcohols with CO2. This research offers an effective approach for the solvent-guided synthesis of MOFs materials and also presents the great application value of MOFs in CO2 chemical conversion.

14.
Mikrochim Acta ; 186(5): 291, 2019 04 23.
Artículo en Inglés | MEDLINE | ID: mdl-31016395

RESUMEN

Nanosheets of tungsten disulfide (WS2) were used to improve the physicochemical properties of reduced graphene oxide aerogel (rGA). The nanosheets were directly integrated into 3D hybrid architecture of rGA by a solvothermal mixing method by which the WS2 sheets were assembled onto the conductive graphene network. WS2 with highly exfoliated and defect-rich structure made the WS2/rGA composite possess plentiful active sites, and this enhanced the electrocatalytic capability of the composite. The introduction of poorly conductive WS2 into 3D rGA system decreases the background current of rGA when used as electrode material. This is advantageous in terms of signal to-noise ratio and analytical performance in general. The WS2/rGA electrode, best operated at a potential of 0.68 V (vs. SCE) has a linear response in the 0.01 to 130 µM nitrite concentration range with a low detection limit of 3 nM (at S/N = 3). It is selective, reproducible, stable and is successfully applied to the determination of nitrite in spiked bacon samples. Graphical Abstract Schematic presentation of an electrochemically modified electrode for the detection of nitrite based on 3D tungsten disulfide/reduced graphene oxide aerogel (WS2/rGA).

15.
Neurol Sci ; 39(6): 1117-1119, 2018 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-29511962

RESUMEN

Uric acid has neuroprotective properties in experimental and clinical studies of neurodegenerative disease. It is, however, associated with increased risk of stroke, yet, despite some inconsistent findings, increasing evidence suggests it may also be related to improved stroke outcomes. We have determined whether there is an effect of plasma uric acid on the short-term outcome of stroke patients in a general hospital setting using the modified Rankin Scale (mRS). We also investigated the relationship of uric acid with other clinical correlates. Plasma uric acid was determined in 108 acute ischemic stroke patients and their mRS scores measured. Patients with a poor outcome (mRS > 2) had significantly lower uric acid than those with a better outcome; this remained after correcting for the effect of sex on uric acid concentrations. There was no significant association with other epidemiological factors or with cognitive function determined by Mini-Mental State Examination. An association between uric acid and the cerebral circulation was also found in which lower uric acid occurs with posterior artery involvement. These findings demonstrate in a naturalistic cohort of patients the association of uric acid with short-term disability following ischemic stroke. They also raise the question of whether uric acid may influence the regional brain involvement in stroke.


Asunto(s)
Isquemia Encefálica/sangre , Accidente Cerebrovascular/sangre , Ácido Úrico/sangre , Anciano , Biomarcadores/sangre , Isquemia Encefálica/complicaciones , Circulación Cerebrovascular , Estudios de Cohortes , Estudios Transversales , Femenino , Humanos , Modelos Logísticos , Masculino , Pruebas de Estado Mental y Demencia , Persona de Mediana Edad , Pronóstico , Índice de Severidad de la Enfermedad , Factores Sexuales , Accidente Cerebrovascular/complicaciones , Factores de Tiempo
16.
Lipids Health Dis ; 17(1): 34, 2018 Feb 27.
Artículo en Inglés | MEDLINE | ID: mdl-29482628

RESUMEN

BACKGROUND: Several mutations in leucine rich repeat kinase 2 (LRRK2) gene have been associated with pathogenesis of Parkinson's disease (PD), a neurodegenerative disorder marked by resting tremors, and rigidity, leading to Postural instability. It has been revealed that mutations that lead to an increase of kinase activity of LRRK2 protein are significantly associated with PD pathogenesis. Recent studies have shown that some Rab GTPases, especially Rab8, serve as substrates of LRRK2 and undergo phosphorylation in its switch II domain upon interaction. Current study was performed in order to find out the effects of the phosphorylation of Rab8 and its mutants on lipid metabolism and lipid droplets growth. METHODS: The phosphorylation status of Rab8a was checked by phos-tag gel. Point mutant construct were generated to investigate the function of Rab8a. 3T3L1 cells were transfected with indicated plasmids and the lipid droplets were stained with Bodipy. Fluorescent microscopy experiments were performed to examine the sizes of lipid droplets. The interactions between Rab8a and Optineurin were determined by immunoprecipitation and western blot. RESULTS: Our assays demonstrated that Rab8a was phosphorylated by mutated LRRK2 that exhibits high kinase activity. Phosphorylation of Rab8a on amino acid residue T72 promoted the formation of large lipid droplets. T72D mutant of Rab8a had higher activity to promote the formation of large lipid droplets compared with wild type Rab8a, with increase in average diameter of lipid droplets from 2.10 µm to 2.46 µm. Moreover, phosphorylation of Rab8a weakened the interaction with its effector Optineurin. CONCLUSIONS: Y1699C mutated LRRK2 was able to phosphorylate Rab8a and phosphorylation of Rab8a on site 72 plays important role in the fusion and enlargement of lipid droplets. Taken together, our study suggests an indirect relationship between enhanced lipid storage capacity and PD pathogenesis.


Asunto(s)
Metabolismo de los Lípidos , Proteínas de la Membrana/metabolismo , Proteínas de Unión al GTP rab/metabolismo , Células 3T3-L1 , Animales , Proteínas de Ciclo Celular , Humanos , Gotas Lipídicas/metabolismo , Proteínas de la Membrana/genética , Proteínas de Transporte de Membrana , Ratones , Mutación , Enfermedad de Parkinson/metabolismo , Factor de Transcripción TFIIIA/metabolismo , Tirosina/genética , Tirosina/metabolismo , Proteínas de Unión al GTP rab/genética
17.
Chemistry ; 23(54): 13289-13293, 2017 Sep 27.
Artículo en Inglés | MEDLINE | ID: mdl-28758267

RESUMEN

A novel metal-organic framework {[Zn(XL)2 ](ClO4 )2 ⋅6 H2 O}n (XL=N,N'-bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxdiimide bi(1,2,4-triazole)) was synthesized and structurally characterized, presenting the first example of six-fold interpenetrating 3 D framework with the topology type of sqc6, which displays high thermostability and solvent stability. Additionally, the luminescence investigations reveal that this MOF can sensitively and selectively detect acetylacetone with a detection limit of 1.72 ppm. More importantly, it is rather rare for an MOF-based luminescence probe to serve as a sensor to effectively detect acetylacetone.

18.
Phys Chem Chem Phys ; 19(46): 31443-31451, 2017 Nov 29.
Artículo en Inglés | MEDLINE | ID: mdl-29159355

RESUMEN

The joint computational and experimental efforts reveal that the organic molecule 1,2-diisocyano-4,5-dimethylbenzene (1) acts as both a reactant and a photosensitizer (PS) in a metal-free reaction with perfluoroalkylhalide (2) to produce 2-perfluoroalkyl quinoxalines (3) under visible light. Both the π-π stacking aggregation in crystals and the solvation in various solvents of PS 1 exhibited visible-light absorption at 466 nm in spite of its smaller coefficient than that of the ultraviolet-light absorption. Such an aggregation-assisted visible-light absorption phenomenon is rationalized by theoretical calculations of the condensed-phase properties with the consideration of the explicit polarization effect from the neighboring molecules. Upon irradiation with different wavelengths, the emission colors changed from navy to bright yellow. Fluorescence lifetime measurements show that the emission of 1 comes from its singlet excited state. The aggregation induced emission when excited at 420 nm has a shorter lifetime (0.45 ns) than that of the emission from isolated molecules (2.71 ns) when excited at 381 nm. It is conceived that the aggregation assisted visible light absorption properties may be general in other photo-reactive molecules, such as 1,4-diisocyano-2,5-dimethylbenzene (4), 1,4-dicyanobenzene (5), and 1,4-diisocyanobenzene (6), which are widely used in many photochemical reactions in the absence of any external photosensitizer.

19.
Anal Biochem ; 500: 80-7, 2016 May 01.
Artículo en Inglés | MEDLINE | ID: mdl-26898304

RESUMEN

In this article, a novel, label-free, and inherent electroactive redox immunosensor for carcinoembryonic antigen (CEA) based on gold nanoparticles (AuNPs) and Nile blue A (NB) hybridized electrochemically reduced graphene oxide (NB-ERGO) is proposed. The composite of NB-graphene oxide (NB-GO) was prepared by π-π stacking interaction. Then, chronoamperometry was adopted to simultaneously reduce HAuCl4 and nanocomposites of NB-GO for synthesizing AuNPs/NB-ERGO. The immunosensor was fabricated by capturing CEA antibody (anti-CEA) at this nanocomposite modified electrode. The immunosensor determination was based on the fact that, due to the formation of antigen-antibody immunocomplex, the decreased response currents of NB were directly proportional to the concentrations of CEA. Under optimal conditions, the linear range of the proposed immunosensor was estimated to be from 0.001 to 40 ng ml(-1) and the detection limit was estimated to be 0.00045 ng ml(-1). The proposed immunosensor was used to determine CEA in clinical serum samples with satisfactory results. The proposed method may provide promising potential application in clinical immunoassays with the properties of facile procedure, stability, high sensitivity, and selectivity.


Asunto(s)
Técnicas Biosensibles , Antígeno Carcinoembrionario/análisis , Técnicas Electroquímicas/instrumentación , Grafito/química , Nanocompuestos/química , Oxazinas/química , Microscopía Electrónica de Rastreo , Óxidos/química
20.
Inorg Chem ; 55(17): 8898-904, 2016 Sep 06.
Artículo en Inglés | MEDLINE | ID: mdl-27560459

RESUMEN

Five tetranuclear rare-earth complexes, [RE4(dbm)4L6(µ3-OH)2] [HL = 5- (4-fluorobenzylidene)-8-hydroxylquinoline; dbm = 1,3-diphenyl-1,3-propanedione; RE = Y (1), Eu (2), Tb (3), Dy (4), Lu (5)], have been synthesized and completely characterized. The X-ray structural analyses show that each [RE4] complex is of typical butterfly or rhombus topology. Each RE(III) center exists in an eight-coordinated square-antiprism environment. Magnetic studies reveal that complex 4 displays single-molecule-magnet behavior below 10 K under a zero direct-current field, with an effective anisotropy barrier (ΔE/kB = 56 K). The fluorescence properties of complexes 1-5 were also investigated. Complexes 2-4 showed their characteristic peaks for the corresponding RE(III) center, while complexes 1 and 5 showed the same emission peaks with the ligand when they were excited at the same wavelength.

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