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1.
Nano Lett ; 24(3): 881-889, 2024 Jan 24.
Artículo en Inglés | MEDLINE | ID: mdl-38198246

RESUMEN

Cellulose nanofiber (CNF) possesses excellent intrinsic properties, and many CNF-based high-performance structural and functional materials have been developed recently. However, the coordination of the mechanical properties and functionality is still a considerable challenge. Here, a CNF-based structural material is developed by a bioinspired gradient structure design using hollow magnetite nanoparticles and the phosphorylation-modified CNF as building blocks, which simultaneously achieves a superior mechanical performance and electromagnetic wave absorption (EMA) ability. Benefiting from the gradient design, the flexural strength of the structural material reached ∼205 MPa. Meanwhile, gradient design improves impedance matching, contributing to the high EMA ability (-59.5 dB) and wide effective absorption width (5.20 GHz). Besides, a low coefficient of thermal expansion and stable storage modulus was demonstrated as the temperature changes. The excellent mechanical, thermal, and EMA performance exhibited great potential for application in stealth equipment and electromagnetic interference protecting electronic packaging materials.

2.
Inorg Chem ; 63(24): 11347-11353, 2024 Jun 17.
Artículo en Inglés | MEDLINE | ID: mdl-38813991

RESUMEN

Two lanthanide 3D coordination polymers [Ln2(L)4Cl2(H2O)4]n (Ln = Eu (1), Gd (2)) with quinoline-2-carboxylic acid (HL) as the ligand were successfully synthesized and characterized. Complex 1 exhibits a highly sensitive and selective luminescent response to 2,6-dipicolinic acid (DPA) in tap water and is virtually unaffected by interferences such as amino acids, aromatic carboxylic acids, and ions. With the addition of DPA, the luminescence intensity of complex 1 decreases rapidly to the naked eye. The detection limit of 1 toward DPA is 3.36 µM, which is much less than the infectious dose (60 µM) of the anthrax spores, indicating the high sensitivity of 1 to DPA. This study offers a basis for employing lanthanide complexes in real sample analysis, enabling direct and efficient detection of DPA with high sensitivity and specificity. Additionally, it is noteworthy that at a magnetic field strength of 7 T and a temperature of 3 K, the maximum entropy change for complex 2 attains a value of 23.56 J kg-1 K-1.

3.
Bioorg Chem ; 150: 107560, 2024 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-38878752

RESUMEN

Leveraging the elevated hydrogen peroxide (H2O2) levels in cancer cells, H2O2-activated prodrugs have emerged as promising candidates for anticancer therapy. Notably, the efficacy of these prodrugs is influenced by the varying H2O2 levels across different cancer cell types. In this context, we have developed a novel H2O2-activated prodrug, PBE-AMF, which incorporates a phenylboronic ester (PBE) motif. Upon H2O2 exposure, PBE-AMF liberates the fluorescent and cytotoxic molecule amonafide (AMF), functioning as a theranostic agent. Our studies with PBE-AMF have demonstrated a positive correlation between intracellular H2O2 concentration and anticancer activity. The breast cancer cell line MDA-MB-231, characterized by high H2O2 content, showed the greatest susceptibility to this prodrug. Subsequently, we replaced the PBE structure with phenylboronic acid (PBA) to obtain the prodrug PBA-AMF, which exhibited enhanced stability, aqueous solubility, and tumor cell selectivity. This selectivity is attributed to its affinity for sialic acid, which is overexpressed on the surfaces of cancer cells. In vitro assays confirmed that PBA-AMF potently and selectively inhibited the proliferation of MDA-MB-231 cells, while sparing non-cancerous MCF-10A cells. Mechanistic investigations indicated that PBA-AMF impedes tumor proliferation by inhibiting DNA synthesis, reducing ATP levels, inducing apoptosis, and arresting the cell cycle. Our work broadens the range of small molecule H2O2-activated anticancer theranostic prodrugs, which are currently limited in number. We anticipate that the applications of PBA-AMF will extend to a wider spectrum of tumors and other diseases associated with increased H2O2 levels, thereby offering new horizons in cancer diagnostics and treatment.


Asunto(s)
Antineoplásicos , Proliferación Celular , Ensayos de Selección de Medicamentos Antitumorales , Peróxido de Hidrógeno , Profármacos , Profármacos/química , Profármacos/farmacología , Profármacos/síntesis química , Humanos , Peróxido de Hidrógeno/farmacología , Antineoplásicos/farmacología , Antineoplásicos/química , Antineoplásicos/síntesis química , Proliferación Celular/efectos de los fármacos , Estructura Molecular , Relación Estructura-Actividad , Apoptosis/efectos de los fármacos , Relación Dosis-Respuesta a Droga , Nanomedicina Teranóstica , Línea Celular Tumoral , Supervivencia Celular/efectos de los fármacos , Ácidos Borónicos/química , Ácidos Borónicos/farmacología , Ácidos Borónicos/síntesis química , Adenina , Organofosfonatos
4.
Hepatology ; 76(6): 1690-1705, 2022 12.
Artículo en Inglés | MEDLINE | ID: mdl-35229337

RESUMEN

BACKGROUND AND AIMS: Hepatocyte transplantation has been demonstrated to be effective to treat liver metabolic disease and acute liver failure. Nevertheless, the shortage of donor hepatocytes restrained its application in clinics. To expand human hepatocytes at a large scale, several dedifferentiation-based protocols have been established, including proliferating human hepatocytes (ProliHH). However, the decreased transplantation efficiency of these cells after long-term expansion largely impedes their application. APPROACH AND RESULTS: We found that accompanied with dedifferentiation, long-term cultured ProliHH (lc-ProliHH) up-regulated a panel of chemokines and cytokines related to innate immunity, which were referred to as dedifferentiation-associated inflammatory factors (DAIF). DAIF elicited excessive macrophage responses, accounting for the elimination of lc-ProliHH specifically during engraftment. Two possible strategies to increase ProliHH transplantation were then characterized. Blockage of innate immune response by dexamethasone reverted the engraftment and repopulation of lc-ProliHH to a level comparable to primary hepatocytes, resulting in improved liver function and a better survival of fumarylacetoacetate hydrolase-deficient mice. Alternatively, rematuration of lc-ProliHH as organoids reduced the expression of DAIF and led to markedly improved engraftment. CONCLUSIONS: These results revealed that lc-ProliHH triggers exacerbated macrophage activation by DAIF and provided potential solutions for clinical transplantation of lc-ProliHH.


Asunto(s)
Hepatocitos , Hígado , Humanos , Ratones , Animales , Hepatocitos/metabolismo , Hígado/metabolismo , Citocinas/metabolismo , Quimiocinas/metabolismo , Macrófagos/metabolismo
5.
Angew Chem Int Ed Engl ; 62(6): e202211099, 2023 Feb 01.
Artículo en Inglés | MEDLINE | ID: mdl-36416072

RESUMEN

The oriented pore structure of wood endows it with a variety of outstanding properties, among which the low thermal conductivity has attracted researchers to develop wood-like aerogels as excellent thermal insulation materials. However, the increasing demands of environmental protection have put forward new and strict requirements for the sustainability of aerogels. Here, we report an all-natural wood-inspired aerogel consisting of all-natural ingredients and develop a method to activate the surface-inert wood particles to construct the aerogel. The obtained wood-inspired aerogel has channel structure similar to that of natural wood, endowing it with superior thermal insulation properties to most existing commercial sponges. In addition, remarkable fire retardancy and complete biodegradability are integrated. With the above outstanding performances, this sustainable wood-inspired aerogel will be an ideal substitute for the existing commercial thermal insulation materials.

6.
Inorg Chem ; 61(48): 19097-19105, 2022 Dec 05.
Artículo en Inglés | MEDLINE | ID: mdl-36399365

RESUMEN

A series of di- and tetranuclear lanthanide complexes with the formulas [Dy2bmzch(tmhd)5 (CH3OH)]·CH3OH (1), [Dy2bmzch(dbm)4 (CH3O)(CH3OH)]·0.5CH3OH·0.5H2O (2), and Dy4bmzch(btfa)10 (3), where tmhd = 2,2,6,6-tetramethyl-3,5-heptanedionate, dbm = dibenzoylmethane, btfa = benzoyltrifluoroacetone, and bmzch = (Z)-N-[(E)-pyrimidin-2-ylmethylene]pyrimidine-2-carbohydrazonate, were structurally and magnetically characterized. More strikingly, although the nitrogen-enriched bridged ligand 3,6-di(pyrimidin-2-yl)-1,2,4,5-tetrazine (bmtz) was initially adopted, the structures of the complexes obtained indicated that bmtz underwent unprecedented asymmetric ring opening and generated a new ligand bmzch. Combined with different ß-diketonates, di- and tetranuclear dysprosium complexes were constructed in which the structural patterns are very sensitive to the selected ß-diketonates. In view of this, the bilateral and unilateral dinuclear Dy2 complexes 1 and 2 and tetranuclear Dy4 complex 3 were obtained by choosing different ß-diketonates. Magnetic test results reveal that both complexes 1 and 3 showcase typical slow magnetic relaxation behavior without an external direct-current field and the effective energy barrier of the latter is almost twice that of the former, while complex 2 only displays in-field single-molecule-magnetic behavior. Also of note is that these are the first tetrazine-type dysprosium-based single-molecule-magnets undergoing in situ asymmetric ring-opening reaction of this ligand that are formed.

7.
Nanotechnology ; 33(21)2022 Feb 28.
Artículo en Inglés | MEDLINE | ID: mdl-35147518

RESUMEN

To improve the sensitivity for electro-chemiluminescent (ECL) detection of chloramphenicol (CAP), a common broad-spectrum antibiotic, boron nitride quantum dots (BNQDs) were prepared with excellent photoelectric property and low toxicity. After its structure and electrochemical property were investigated in detail, it was noted that the ECL signal of Ru(Phen)32+could be strengthened by the proposed BNQDs, which was further activated by ten's times in the presence of CAP. Under the optimized conditions, there was an excellent linear relationship between ΔECL and lgcCAPin a wide linear range from 1.0 × 10-10to 1.0 × 10-6mol l-1CAP. The detection limit was super-low to be 3.3 × 10-11mol l-1(S/N = 3). When applied for CAP detection in real pharmaceutical and food samples, the recoveries were between 97.8% and 105.7% with R.S.D. less than 3.3%. A possible CAP-activated ECL mechanism of BNQDs-Ru(phen)32+was also proposed. This work will offer a great potential for efficient monitoring of CAP pollution and clinical diagnosing of CAP-related diseases in future.

8.
Nanotechnology ; 2022 Feb 10.
Artículo en Inglés | MEDLINE | ID: mdl-35144249

RESUMEN

To improve the sensitivity for electro-chemiluminescent (ECL) detection of chloramphenicol (CAP), a common broad-spectrum antibiotic, boron nitride quantum dots (BNQDs) were prepared with excellent photoelectric property and low toxicity. After its structure and electrochemical property were investigated in detail, it was noted that the ECL signal of Ru(Phen)32+ could be strengthened by the proposed BNQDs, which was further activated by ten's times in the presence of CAP. Under the optimized conditions, there was an excellent linear relationship between △ECL and lgcCAP in a wide linear range from 1.0×10-10 to 1.0×10-6 mol/L CAP. The detection limit was super-low to be 3.3×10-11 mol/L (S/N=3). When applied for CAP detection in real pharmaceutical and food samples, the recoveries were between 97.8 and 105.7 % with R.S.D. less than 3.3%. A possible CAP-activated ECL mechanism of BNQDs-Ru(phen)32+ was also proposed. This work will offer a great potential for efficient monitoring of CAP pollution and clinical diagnosing of CAP-related diseases in future.

9.
Sensors (Basel) ; 22(20)2022 Oct 13.
Artículo en Inglés | MEDLINE | ID: mdl-36298135

RESUMEN

In recent years, vital signals monitoring in sports and health have been considered the research focus in the field of wearable sensing technologies. Typical signals include bioelectrical signals, biophysical signals, and biochemical signals, which have applications in the fields of athletic training, medical diagnosis and prevention, and rehabilitation. In particular, since the COVID-19 pandemic, there has been a dramatic increase in real-time interest in personal health. This has created an urgent need for flexible, wearable, portable, and real-time monitoring sensors to remotely monitor these signals in response to health management. To this end, the paper reviews recent advances in flexible wearable sensors for monitoring vital signals in sports and health. More precisely, emerging wearable devices and systems for health and exercise-related vital signals (e.g., ECG, EEG, EMG, inertia, body movements, heart rate, blood, sweat, and interstitial fluid) are reviewed first. Then, the paper creatively presents multidimensional and multimodal wearable sensors and systems. The paper also summarizes the current challenges and limitations and future directions of wearable sensors for vital typical signal detection. Through the review, the paper finds that these signals can be effectively monitored and used for health management (e.g., disease prediction) thanks to advanced manufacturing, flexible electronics, IoT, and artificial intelligence algorithms; however, wearable sensors and systems with multidimensional and multimodal are more compliant.


Asunto(s)
COVID-19 , Deportes , Dispositivos Electrónicos Vestibles , Humanos , Inteligencia Artificial , Pandemias , COVID-19/diagnóstico , Monitoreo Fisiológico/métodos
10.
Nanotechnology ; 32(25)2021 Mar 31.
Artículo en Inglés | MEDLINE | ID: mdl-33721849

RESUMEN

In this work, one-dimensional nitrogen doped porous carbon nano-arrays arranged by carbon nanotube (1D CNTs@NPC) were first constructed, using a coating technology at room temperature and followed by high temperature carbonization. It was expected that the resulting glassy carbon electrodes modified by 1D CNTs@NPC (CNTs@NPC/GCE) could express different electrochemical responses to ascorbic acid (AA), dopamine (DA), uric acid (UA), by virtue of the synergistic-improved effect between CNTs and NPC. Under the optimized conditions, there were excellent analytical parameters for CNTs@NPC/GCE to detect AA, DA and UA, i.e. a wide linear range of 40-2100µM for AA, 0.5-49µM for DA and 3-50µM for AA with low detection limits of 0.36µM, 0.02µmol l-1and 0.57µM respectively. Importantly, the proposed CNTs@NPC/GCE was efficiently applied to determine AA, DA and UA in some real samples with high stability, reproducibility and selectivity. This work will offer an efficient potential for diagnosing ascorbic acid, dopamine or uric acid-related diseases on clinical testing in future.


Asunto(s)
Ácido Ascórbico/análisis , Dopamina/análisis , Técnicas Electroquímicas/métodos , Nanotubos de Carbono/química , Ácido Úrico/análisis , Límite de Detección , Nitrógeno/química , Porosidad
11.
Sensors (Basel) ; 21(17)2021 Sep 02.
Artículo en Inglés | MEDLINE | ID: mdl-34502799

RESUMEN

Social distancing protocols have been highly recommended by the World Health Organization (WHO) to curb the spread of COVID-19. However, one major challenge to enforcing social distancing in public areas is how to perceive people in three dimensions. This paper proposes an innovative pedestrian 3D localization method using monocular images combined with terrestrial point clouds. In the proposed approach, camera calibration is achieved based on the correspondences between 2D image points and 3D world points. The vertical coordinates of the ground plane where pedestrians stand are extracted from the point clouds. Then, using the assumption that the pedestrian is always perpendicular to the ground, the 3D coordinates of the pedestrian's feet and head are calculated iteratively using collinear equations. This allows the three-dimensional localization and height determination of pedestrians using monocular cameras, which are widely distributed in many major cities. The performance of the proposed method was evaluated using two different datasets. Experimental results show that the pedestrian localization error of the proposed approach was less than one meter within tens of meters and performed better than other localization techniques. The proposed approach uses simple and efficient calculations, obtains accurate location, and can be used to implement social distancing rules. Moreover, since the proposed approach also generates accurate height values, exclusionary schemes to social distancing protocols, particularly the parent-child exemption, can be introduced in the framework.


Asunto(s)
COVID-19 , Peatones , Calibración , Pie , Humanos , SARS-CoV-2
12.
Entropy (Basel) ; 23(10)2021 Sep 29.
Artículo en Inglés | MEDLINE | ID: mdl-34682002

RESUMEN

Opportunistic beamforming (OBF) is a potential technique in the fifth generation (5G) and beyond 5G (B5G) that can boost the performance of communication systems and encourage high user quality of service (QoS) through multi-user selection gain. However, the achievable rate tends to be saturated with the increased number of users, when the number of users is large. To further improve the achievable rate, we proposed a multi-antenna opportunistic beamforming-based relay (MOBR) system, which can achieve both multi-user and multi-relay selection gains. Then, an optimization problem is formulated to maximize the achievable rate. Nevertheless, the optimization problem is a non-deterministic polynomial (NP)-hard problem, and it is difficult to obtain an optimal solution. In order to solve the proposed optimization problem, we divide it into two suboptimal issues and apply a joint iterative algorithm to consider both the suboptimal issues. Our simulation results indicate that the proposed system achieved a higher achievable rate than the conventional OBF systems and outperformed other beamforming schemes with low feedback information.

13.
Entropy (Basel) ; 23(7)2021 Jun 25.
Artículo en Inglés | MEDLINE | ID: mdl-34202070

RESUMEN

Opportunistic beamforming (OBF) is an effective technique to improve the spectrum efficiencies (SEs) of multiple-input-multiple-output (MIMO) systems, which can obtain multiuser diversity gains with both low computation complexity and feedback information. To serve multiple users simultaneously, many multiple-access schemes have been researched in OBF. However, for most of the multiple-access schemes, the SEs are not satisfactory. To further improve the SE, this paper proposes a downlink multiuser OBF system, where both orthogonal frequency division multiplexing (OFDM) and non-orthogonal multiple-access (NOMA) methods are applied. The closed-form expressions of the equivalent channels and SE are derived in frequency selective fading channels. Then, an optimization problem is formulated to maximize the SE, although the optimization problem is non-convex and hard to solve. To obtain the solution, we divide the optimization problem into two suboptimal issues, and then a joint iterative algorithm is applied. In the proposed optimization scheme, the subcarrier mapping ϑ, user pairing knc and allocated power Pknc are determined to maximize spectrum efficiency (SE) and reduce bit error ratio (BER). According to numerical results, the proposed method achieves approximately 5 dB gain on both SE and BER, compared to the existing beamforming methods with low feedback information. Moreover, the SE of the proposed method is approximately 2 (bps/Hz) higher than sparse code multiple-access (SCMA), when the number of waiting users and the ratio of transmit power to noise variance are respectively 10 and 20 dB. It is indicated that the proposed scheme can achieve high and low BER with the limited feedback and computation complexity, regardless of the transmit power and the number of waiting users.

14.
Mediators Inflamm ; 2020: 7280708, 2020.
Artículo en Inglés | MEDLINE | ID: mdl-32454793

RESUMEN

BACKGROUND: This study is aimed at investigating whether albumin-to-fibrinogen ratio (AFR) could independently predict the prognosis in patients with peritonitis-induced sepsis. METHODS: A total of 246 eligible patients who were scheduled to undergo surgical treatment for peritonitis-induced sepsis were enrolled in this study. The primary observational endpoint was 28-day hospital mortality. Cox proportional hazards regression analysis with the Wald test was performed to identify prognostic factors for 28-day mortality in septic patients. Receiver operating characteristic (ROC) and Kaplan-Meier curve analyses were carried out to evaluate the association of baseline AFR and prognosis in septic patients. RESULTS: Of all the cohort study participants, there were 59 nonsurvivors with a 28-day mortality of 24.0% (59/246). Baseline AFR (hazard ratio (HR): 0.67, 95% confidence interval (CI): 0.42-0.93, P = 0.018) and the presence of septic shock (HR: 2.43, 95% CI: 1.42-3.91, P = 0.021) were two independent prognostic factors for 28-day mortality in patients with peritonitis-induced sepsis by multivariate Cox analysis. Baseline AFR was a significant predictor for 28-day mortality with an area under the curve (AUC) of 0.751, a cut-off value of 8.85, a sensitivity of 66.10%, and a specificity of 70.05%, respectively (95% CI: 0.688-0.813, P < 0.001). A low baseline AFR level (≤8.85) was significantly associated with a lower overall survival rate in septic patients by Kaplan-Meier curve analysis with log-rank test (P = 0.004). CONCLUSIONS: This study indicates that AFR independently predicts 28-day mortality in patients with peritonitis-induced sepsis.


Asunto(s)
Albúminas/análisis , Fibrinógeno/análisis , Peritonitis/complicaciones , Sepsis/complicaciones , Sepsis/mortalidad , Anciano , Anciano de 80 o más Años , Femenino , Humanos , Estimación de Kaplan-Meier , Masculino , Persona de Mediana Edad , Peritonitis/microbiología , Pronóstico , Modelos de Riesgos Proporcionales , Estudios Retrospectivos , Factores de Riesgo , Sepsis/microbiología , Choque Séptico/sangre
15.
Inorg Chem ; 57(14): 8332-8337, 2018 Jul 16.
Artículo en Inglés | MEDLINE | ID: mdl-29943980

RESUMEN

Chiral lanthanide helical architectures have received intense attentions in recent years because of their potential applications as chiral probes and sensors and as circularly polarized luminescence (CPL) materials. However, stereoselectivity control in the self-assembly of lanthanide helicate is challenging due to the poor stereochemical preference and variable coordination numbers of Ln(III) ions. Herein, we reported the employing chiral ancillary ligand R/S-BINAPO to induce achiral tripodal ligand to form a pair of homochiral lanthanide triple-helical podates [Eu(TTEA)((R/S)-BINAPO); R/S-1] {(R/S)-BINAPO = ( R/ S)-2,2'-bis(diphenylphosphoryl)-1,1'-binaphthyl; TTEA = tris[(4-(4,4,4-trifluoro-1,3-dioxobutyl)-benzamido)ethyl]amine}. X-ray crystallographic analysis for rac-1 reveals that the chirality of BINAPO is transferred during the self-assembly process to give either P or M helical architectures in podates. The 1H and 31P NMR and circular dichroism measurements confirm the diastereopurity of the assemblies in solution. A detailed optical and chiroptical characterization reveals that the luminescent enantiopure podates not only exhibit intense CPL with | glum| values reaching 0.072 but also show high luminescence quantum yields of 32.8%. Our results provide a feasible strategy for designing homochiral helical lanthanide supramolecular architecture and synthesizing excellent CPL materials.

16.
Inorg Chem ; 57(14): 8065-8077, 2018 Jul 16.
Artículo en Inglés | MEDLINE | ID: mdl-29965732

RESUMEN

A series of Salen-type Zn(II)-Dy(III) complexes [L1Zn(II)ClDy(III)(acac)2]·H2O (1), [L1Zn(II)BrDy(III)(acac)2]·H2O (2), [L1Zn(II)(H2O)Dy(III)(acac)2]·CH2Cl2·PF6 (3), [L2Zn(II)(H2O)Dy(III)(acac)2]·PF6 (4), and Co(III)-Dy(III) complexes [L1Co(III)Br2Dy(III)(acac)2]·CH2Cl2 (5), [L2Co(III)Cl2Dy(III)(acac)Cl(MeO)] (6), [L2Co(III)Cl2Dy(III)(acac)Cl(H2O)] (7), and [L2Co(III)Cl2Dy(III)(NO3)2(MeO)] (8) heterobinuclear single-molecule magnets (SMMs) were synthesized and magnetically characterized. These complexes were constructed by incorporating diamagnetic Zn(II) and Co(III) ions with acetylacetone (acac) and compartmental Schiff-base ligands (H2L1 = N, N'-bis(2-oxy-3-methoxybenzylidene)-1,2-phenylenediamine; H2L2 = N, N'-bis(2-oxy-3-methoxybenzylidene)-1,2-diaminocyclohexane). In the Zn(II)-Dy(III) (1-4) system, the coordination environments of the Dy(III) ions are nearly identical, but the apical coordination atom to the Zn(II) ion is different. Complexes 1, 2, and 4 displayed no magnetic relaxation in the absence of external magnetic field, but complex 3 displayed more pronounced SMM behavior with a relaxation energy barrier Ueff/ kB 38 K and magnetic hysteresis at 1.8 K. The SMM performances of 5, 6, and 7 were enhanced significantly by incorporating an octahedral Co(III) instead of square-pyramidal Zn(II) and replacing one of acac- group around Dy(III) ion by a neutral O atom, displaying Ueff of 167, 118, and 75 K as well as magnetic hysteresis up to 3.5 K. These studies indicated that the remote diamagnetic Zn(II) and Co(III) ions played a key role, and the SMM properties were very strongly related to the special coordination atoms configuration around Dy(III) ion. When this coordination configuration around was broken as 8 exhibited, however, it resulted in a dramatically decreased SMM performance. From this work, the key factors that significantly affect the SMM performance of these heteronuclear Zn(II)/Co(III)-Dy(III) SMMs are unambiguously presented.

17.
Phys Chem Chem Phys ; 17(24): 16136-44, 2015 Jun 28.
Artículo en Inglés | MEDLINE | ID: mdl-26031613

RESUMEN

Two ligands, mono-ß-diketone (p-methoxylbenzoyl)trifluoroacetone (MBTF) and bis-ß-diketone 1,2-bis(4,4'-bis(4,4,4-trifluoro-1,3-dioxobutyl))phenoxyl ethane (BTPE) with similar chemical structures, have been designed and prepared for the purpose of building the relationship between the structures and luminescence properties of Eu(iii) complexes. Structures of the Eu(iii) complexes [Eu(MBTF)3(DMSO)(H2O)] and [Eu2(BTPE)3(DMSO)4] have been defined by single crystal X-ray crystallography. The mono-ß-diketone complex [Eu(MBTF)3(DMSO)(H2O)] is a mononuclear structure, the central Eu(iii) ion is coordinated by eight oxygen atoms from three ligands and two solvents, in a distorted trigonal-dodecahedral (8-TDH) geometry. Whereas, the bis-ß-diketone complex [Eu2(BTPE)3(DMSO)4] adopts a triple-stranded dinuclear structure in which the two Eu(iii) ions are helically wrapped by three bis-bidentate ligands, and each Eu(iii) ion is eight-coordinated by six oxygen atoms from the ligands and two oxygen atoms from the coordinated DMSO molecules, in a distorted square-antiprismatic (8-SAP) geometry. The photophysical properties related to the electronic transition are characterized by the absorbance spectra, the emission spectra, the emission quantum yields, the emission lifetimes, and the radiative (kr) and nonradiative rate constants (knr). The mono-ß-diketone complex [Eu(MBTF)3(DMSO)(H2O)] offers a relatively high emission quantum yield (38%, in solid) compared to that observed in the bis-ß-diketone complex [Eu2(BTPE)3(DMSO)4] (25%, in solid). This enhancement of emission quantum yield in the mono-ß-diketone complex can be attributed to its lower site symmetry around the Eu(iii) ion, lower non-radiative rate constant and higher energy transfer efficiency from the ligand to the metal ion.


Asunto(s)
Complejos de Coordinación/química , Europio/química , Cetonas/química , Complejos de Coordinación/síntesis química , Cristalografía por Rayos X , Cetonas/síntesis química , Ligandos , Luminiscencia , Modelos Moleculares , Estructura Molecular , Procesos Fotoquímicos
18.
Phys Chem Chem Phys ; 17(45): 30510-7, 2015 Nov 11.
Artículo en Inglés | MEDLINE | ID: mdl-26513394

RESUMEN

A bis-ß-diketone, bis(4,4,4-trifluoro-1,3-dioxobutyl)(2,2'-bithienyl) (BTT), which can be looked upon as coupling of two mono-ß-diketones (2-thenoyltrifluoroacetone, TTA) at the 5,5'-position of thiophene ring, has been designed for exploring the advantages of binuclear helical structure in sensitizing the lanthanide NIR luminescence. The Yb(iii) ion was selected as the luminescent center, and its corresponding mono-ß-diketone complex Yb(TTA)3(DMSO) () and bis-ß-diketone complex Yb2(BTT)3(DMSO)4 () were synthesized and isolated. X-ray crystallographical analysis reveals that the bis-ß-diketone complex Yb2(BTT)3(DMSO)4 adopts a triple-stranded dinuclear structure, in which the two Yb(iii) ions are helically wrapped by three ligands, and each Yb(iii) ion is eight-coordinated by six oxygen atoms from three ligands and two oxygen atoms from the coordinated DMSO molecules. Whereas, the mono-ß-diketone complex Yb(TTA)3(DMSO) is a mononuclear structure, the central Yb(iii) ion is coordinated by seven oxygen atoms from three ligands and a DMSO molecule. The photophysical properties related to the electronic transition are characterized by the absorbance spectra, the emission spectra, the emission quantum yields, the emission lifetimes, and the radiative (kr) and nonradiative rate constants (knr). The luminescence quantum yield experiment reveals that the dinuclear complex has about 10 times luminescence enhancement compared with the mononuclear complex. This enhancement mainly benefits from its helical structure, which effectively depresses the nonradiative transition caused by high-energy oscillators in ligands, and the part-encapsulated structure decreases the probability of solvents entering the metal centers.


Asunto(s)
Luminiscencia , Compuestos Organometálicos/química , Iterbio/química , Cetonas/química , Estructura Molecular , Compuestos Organometálicos/síntesis química
19.
Health Mark Q ; 31(1): 46-64, 2014.
Artículo en Inglés | MEDLINE | ID: mdl-24617722

RESUMEN

Weather and its fluctuations have been found to influence the consumption of negative hedonic goods. However, such findings are of limited use to health marketers who cannot control the weather, and hence, its effects. The current research utilizes data obtained at the zip-code level to study geographical variations in the effect of weather on tobacco consumption across the entire continental United States. The results allow health marketers to identify areas that will be most responsive to marketing efforts aimed at curtailing negative hedonic consumption and thus implement more effective, region-specific initiatives.


Asunto(s)
Comercialización de los Servicios de Salud , Uso de Tabaco/epidemiología , Tiempo (Meteorología) , Geografía , Uso de Tabaco/efectos adversos , Uso de Tabaco/economía , Uso de Tabaco/prevención & control , Cese del Uso de Tabaco , Estados Unidos
20.
Environ Sci Pollut Res Int ; 31(14): 22038-22054, 2024 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-38400969

RESUMEN

A comprehensive understanding of the terrestrial carbon sink is essential for proficient regional carbon management. However, previous studies predominantly relied on net ecosystem productivity (NEP) as an indicator of regional carbon sink, overlooking the impacts of carbon emissions from physical processes and carbon leakage associated with anthropogenic activities. In this study, net region productivity (NRP), a vital metric representing carbon sink dynamics in regional multi-landscape ecosystems, was employed to systematically analyze the patterns, trends, and causes of carbon sink in Ordos. The results revealed that spatially averaged NRP in Ordos was 70.334 g·m-2·a-1, indicating a carbon sink effect. The coefficient of variation of NRP was 68.035%, with a higher NRP in the southern region. Normalized difference vegetation index (NDVI) predominantly controlled the spatial heterogeneity of NRP in Ordos, while precipitation emerged as the primary climatic factor influencing spatial differences in NRP. Regional variations in the impact of environmental factors on NRP were evident. In most areas, NRP showed a notable increasing trend influenced by various factors. Specifically, the simultaneous rise in NDVI and improvements in hydrothermal conditions contributed to the gradual elevation of NRP, each with varying degrees of influence across Ordos and its sub-regions.


Asunto(s)
Secuestro de Carbono , Ecosistema , China , Carbono/análisis , Causalidad
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