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To elucidate the luminescence mechanism of highly efficient blue Cu(N^N)(POP)+-type thermally activated delayed fluorescence (TADF) materials, we have selected Cu(pytfmpz)(POP)+ (1) and Cu(pympz)(POP)+ (2) as targets to investigate the photophysical properties in both solution and solid phases. The self-consistent electrostatic potential (ESP) embedded charge within the quantum mechanics/molecular mechanics (QM/MM) method demonstrates a greater advantage over the charge equilibrium (QEQ) in accurately calculating atomic charges and reasonably describing the polarization effect, ultimately resulting in a favorable consistency between simulation and experimental measurements. After systematic and quantitative simulation, it has been found that complex 2, with an electron-donating group of -CH3, exhibits a much more blue-shifted spectrum and a significantly enhanced efficiency in comparison to complex 1 with -CF3. This is due to the widened HOMO-LUMO gap as well as the narrowed energy gap between the lowest singlet and triplet excited states (ΔEST), respectively. Then, the designed complex 3 is introduced with a stronger electron donor and larger tert-butyl group, which plays a key role in simultaneously suppressing the structural distortion and reducing the ΔEST. This leads to a faster reverse intersystem crossing process than that of the two experimental complexes in solution, turning out to be a new deep-blue-emitting material with excellent TADF performance.
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The high incidence and difficulties of treatment of cancer have always been a challenge for mankind. Two-photon photodynamic therapy (TP-PDT) as a less invasive technique provides a new perspective for tumor treatment due to its low-energy near-infrared excitation, high targeting, and minor damage. At present, the emerging metal complexes used as the photosensitizers (PSs) in TP-PDT have aroused great interest. However, most metal complexes as PSs in TP-PDT still face some problems, such as slow clearance, unsatisfactory two-photon absorption (TPA) characteristics, high price, low reactivity, and poor solubility. In this work, density functional theory and time-dependent density functional theory were used to characterize the one/two-photon response, solvation free energy, and lipophilicity of a series of novel PSs applied in TP-PDT. The results suggest that based on complex 1, replacing Ru(II) center with Zn(II) (complex 2) can effectively prolong the triplet excited state lifetime while reducing the cost and environmental pollution, and the azetidine heterospirocycles were introduced into the ligand scaffold (complex 3), which effectively reduced the vibration relaxation of the ligand group and improved the water solubility; further, the addition of acetylenyl groups subtly enhanced the light absorption and significantly improved the two-photon response (complex 4). In addition, all complexes met the requirement of a PS and could be used as potential candidates for TP-PDT. In particular, complex 4 has the advantages of high solvation free energy, a large TPA cross-section (1413 GM), a long triplet state lifetime (671 µs), good chemical reactivity, and low cost, and it is easy to be scavenged by organisms. Overall, this contribution may provide an important clue to formulate clear design principles for type I/II PSs and rational design of PSs with high intersystem crossing rates, a long lifetime, and therapeutic excitation wavelengths.
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Complejos de Coordinación , Fotoquimioterapia , Fármacos Fotosensibilizantes/farmacología , Complejos de Coordinación/farmacología , Ligandos , ZincRESUMEN
Hypochloric acid (HOCl) plays a vital role in the natural defense system, but abnormal levels of it can cause cell damage, accelerated human aging, and various diseases. It is of great significance to develop new probes for detecting HOCl in biosystems nondestructively and noninvasively. The purpose of this work is to explore new chemical modification strategies of two-photon excitation fluorescence (TPEF) probes to improve the poor water solubility and low efficiency in imaging applications. Nil-OH-6 has a two-photon absorption cross-section value as high as 243 GM and attains a good quantum yield of 0.49. In addition, the modification of terminal groups with different azetidine-heterospirocycles or N,N-dialkyl fused amino groups to Nile Red can effectively improve the fluorescence efficiency as well as increase the solubility to some extent. This study provides some strategies to simultaneously improve the fluorescence performance and solubility of these two-photon probes and, hence, reliable guidance and a foundation for the subsequent synthesis of TPEF probes based on Nile Red.
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Colorantes Fluorescentes , Modelos Teóricos , Humanos , Oxazinas , Solubilidad , AguaRESUMEN
To develop solid-state light-emitting materials with high luminescence efficiency, determining the potential photophysics and luminescence mechanisms of the aggregation state remains a challenge and a priority. Here, we apply density functional theory to study the photophysical properties of a series of square planar Pt(ii) complexes in both monomeric and dimeric forms. We reveal that four monomeric Pt(ii) complexes are dominated by triplet ligand-to-ligand charge-transfer, and the lack of the triplet metal-to-ligand charge-transfer feature results in weak spin-orbit coupling (SOC), which leads to limited radiative rates; moreover, calculated nonradiative transition rates are one or two orders of magnitude higher than those radiative rates because a large amount of reorganization energy caused by the vibration of the bipyrazolate (bipz) ligand cannot be readily suppressed in the monomeric form. Therefore, four monomers exhibit photoluminescence quenching in CH2Cl2 solution in both theoretical calculations and experiments. However, in the solid state, the intense luminescence phenomenon indicates obviously distinct properties between the monomer and aggregation. We carried out a dimer model to interpret that the interaction of PtPt induces a metal-metal-to-ligand charge-transfer excimeric state, which leads more metal components to participate in the charge transfer and enhance the SOC effect. At the same time, the ligand vibration can be significantly reduced by the shortened distance, and there is a strong π-π packing interaction in the dimer; thus, an excellent quantum yield can be achieved in aggregation. In addition, we disclose that introducing bulky substituents bearing electron-donating groups at R' and R'' positions have little effect on the properties of the monomers; however, there is a benefit of restricting the internal reorganization energy through the intermolecular interaction when packing in the solid state. Therefore, substitutions can be tuned to improve the properties of monomers (such as emission energy and reorganization energy). We hope that our work will shine some light on Pt(ii) emitters in the fabrication of efficient OLEDs.
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Investigation of the clear structure-property relationship and microscopic mechanism of thermally activated delayed fluorescence (TADF) emitters with high emission quantum yield is a direction worthy of continuous efforts. The instructive theoretical principle of TADF material design is critical and challenging. Here, we carried out theoretical calculation on two experimental Cu(I) complexes with the same 7,8-bis(diphenylphosphino)-7,8-dicarba-nido-undecaborate (dppnc) but different N^N ligands [dmbpy = 6,6'-dimethyl-2,2'-bipyridine (1) or dmp = 2,9-dimethyl-1,10-phenanthroline (2)] to briefly elaborate the structure-TADF performance relationship and luminescence mechanism. It was found that enhanced rigidity by the fused benzene ring between two pyridyl units in complex 2 leads to (i) higher allowedness of S1 â S0, (ii) more effective reverse intersystem crossing (RISC), and (iii) better relative stability of the T1 state, which could be responsible for its excellent TADF behavior. Thus, a strategy of extending π conjugation in the N^N ligand could be deduced to further enhance the quantum yield. We validated it and have succeeded in designing analogue complex 4 by extending π conjugation with an electron-withdrawing pyrazinyl. Benefiting from the smaller energy gap (ΔEST) and plunged reorganization energy between the S1 and T1 states, the rate of RISC in complex 4 (1.05 × 108 s-1) increased 2 orders of magnitude relative to that of 2 (5.80 × 106 s-1), showing more superiority of the TADF behavior through a better balance of RISC, fluorescence, and phosphorescence decay. Meanwhile, the thermally activated temperature of 4 is only 165 K, implying that there is a low-energy barrier. All of these indicate that the designed complex 4 may be a potential TADF candidate.
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The transcriptional activity of the SARP19-I1 and vdg3-I1 genes increases over tenfold when Haliotis diversicolor larvae shift from the pelagic to benthic lifestyle, signifying the important role of these genes during abalone metamorphosis. In this study, eight paralogous SARP19 genes and six paralogous vdg3 genes were identified from H. diversicolor transcriptomes. Phylogenetic analyses were performed, and the spatio-temporal expression patterns of these genes were separately determined by quantitative polymerase chain reaction (qPCR) and whole mount in situ hybridization (WMISH). Five SARP19 paralogs and five vdg3 paralogs showed at least a tenfold increase in expression after settlement. Among these differentially expressed genes, three SARP19 paralogs and four vdg3 paralogs were verified as being spatially expressed in the digestive glands of newly settled postlarvae. We proposed that a hypothesis of coevolution between the two gene families might explain the similarities in their expression patterns and their phylogenetics.
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Gastrópodos/crecimiento & desarrollo , Gastrópodos/genética , Animales , Evolución Molecular , Gastrópodos/fisiología , Duplicación de Gen , Metamorfosis Biológica , Filogenia , TranscriptomaRESUMEN
Forest fires are harmful to the ecological environment, which have induced global attention. In the present paper fire activities extracted from MODIS and burned areas were compared, and it was found that the wave band of 8-9 extracted from MOD14A1 was useful for fire monitoring, and the data accorded with field investigation with goodness of fit reaching up to 0. 83. Through combining this wave band and the relative data to make the time and space analysis of the forest fires for 11 years, from 2000 to 2010, the study showed that the fire occurred most frequently in the spring, the autumn took the second place, and in the summer there was almost no fire occurrence unless drought. Through the analysis of the research area, the burned areas of the coniferous forest and temperate mixed forest were 53.68% and 44%, respectively, while the grassland was only 2.32%. Da Hinggan Ling region was the main combustion area, the burned areas were 64.7% and that for Xiao Hinggan Ling was about 23.49%, while those for other areas were less than 5%. The majority of forest land of burned areas has a gentle slope (< or =5 percent), and is in the middle altitude between 200 and 500 m. So, using satellite remote sensing to analyze the time series of burned areas in forests would make the relationship between the fire activities, climate change, topography and vegetation type clear and it is also helpful to predicting the risk level of the fire areas.
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Monitoreo del Ambiente , Incendios , Bosques , Imágenes Satelitales , Sequías , Estaciones del Año , Análisis Espacio-TemporalRESUMEN
Cu(I) complexes have received widespread attention as a promising alternative to traditional noble-metal complexes. Herein, we systematically study the properties of Cu(I) complexes from homo- to hetero-ligands, and found the following: (1) hetero-ligands are beneficial to regulate phosphorescent efficiency; (2) when the hetero-ligands in a tetracoordinated Cu(I) complex are 1:1, the ligands coordinate along the dx2-y2 direction of Cu(I) ion, which can observably suppress structural deformation; (3) unlike the P^P ligand, the N^N ligand can enhance the participation of Cu(I) during the transition process; (4) the addition of an appropriate amount of P^P ligand can effectively raise the energy level of HOMO (highest occupied molecular orbital), enhance the proportion of LLCT (ligand-ligand charge transfer), and thereby increase the available singlet emission transition moments which can be borrowed, thus promoting the radiative decay process. As a result, this work provides a detailed understanding of the effects of different ligands in Cu(I) complexes, and provides a valuable reference and theoretical basis for regulating and designing the phosphorescent properties of Cu(I) complexes in the future.
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Profound understanding of the luminescence mechanism and structure-property relationship is vital for Cu(I) thermally activated delayed fluorescence (TADF) emitters. Herein, we theoretically simulated luminescent behavior in both solution and solid phases for two Cu(I) complexes and found the following: (i) The strengthened spin-orbit coupling (SOC) effect by more dx2-y2 orbital contributions and well-restricted structural distortion via remarkable intramolecular interaction in [Cu(dmp)(POP)]+ enable the emission at room temperature to be a mixture of direct phosphorescence (10%) and TADF (90%). (ii) Benefiting from enhanced steric hindrance and the electron-donating ability of the paracyclophane group, the narrowed S1-T1 energy separation (ΔEST) in [Cu(dmp)(phanephos)]+ accelerates the reverse intersystem crossing, promoting the TADF rate (1.88 × 105 s-1) and intensity ratio (98.3%). These results indicate that the small ΔEST is superior for reducing the lifetime and that the strong SOC stimulates the phosphorescence to compete with TADF, which are both conducive to avoiding collision-induced exciton quenching and reducing the roll-off in devices.
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MicroRNA390 (miR390), an ancient and highly conserved miRNA family in land plants, plays multiple roles in plant growth, development and stress responses. In this study, we isolated and identified MIR390, miR390, TAS3a/b/c, tasiARF-1/2/3 (trans-acting small interfering RNAs influencing Auxin Response Factors) and ARF2/3/4 in Jerusalem artichoke (Helianthus tuberosus L.). Treatment with 100 mM NaCl induced expression of miR390, increased cleavage of TAS3, produced high levels of tasiARFs, and subsequently enhanced cleavage of ARF3/4, which was most likely associated with salt tolerance of the plants. In contrast, treatment with 300 mM NaCl inhibited expression of miR390, attenuated cleavage of TAS3, produced a small amount of tasiARFs, and reduced cleavage of ARF3/4. We proposed that ARF2, one of the targets of tasiARFs, induced under salinity was likely to play an active role in salt tolerance of Jerusalem artichoke. The study of the miR390-TAS3-ARF model in Jerusalem artichoke may broaden our understanding of salt tolerance mechanisms, and provides a theoretical support for further genetic identification and breeding crops with increased tolerance to salt stress.
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Helianthus/metabolismo , MicroARNs/metabolismo , Estrés Salino/fisiología , Regulación de la Expresión Génica de las Plantas , Helianthus/genética , MicroARNs/genética , Raíces de Plantas/genética , ARN de Planta/genética , ARN Interferente Pequeño/genética , Salinidad , Estrés Salino/genética , Tolerancia a la Sal/genéticaRESUMEN
OBJECTIVE: To compare proximal gastrectomy (PG) with total gastrectomy (TG) for proximal gastric carcinoma, through the 5-year survival rate, recurrence rate, postoperative complications, and long-term life quality. METHODS: The meta-analysis was carried out in the General Surgery Department of the Second Affiliated Hospital of Soochow University, Suzhou, Jiangsu Province, China. We searched Medline, EMBASE, and the Cochrane Library from June to November 2012. The literature searches were carried out using medical subject headings and free-text word: `proximal gastrectomy` `total gastrectomy` `partial gastrectomy` `stomach neoplasms` and `gastric cancer`. Two different reviewers carried out the search and evaluated studies independently. RESULTS: Two randomized controlled trials and 9 retrospective studies were included. A total of 1364 patients were included in our study. Our analysis showed that there is no statistically significant difference in 5-year survival rate between PG and TG (60.9% versus 64.4%). But, the recurrence is higher in the PG group than the TG (38.7% versus 24.4%). The anastomotic stenosis rate is also higher in the PG than the TG (27.4% versus 7.4%). CONCLUSION: Proximal gastrectomy is an option for upper third gastric cancer in terms of safety. However, it is associated with high risk of reflux symptoms and anastomotic stenosis. Therefore, TG should be the first choice for proximal gastric cancer to prevent reflux symptoms.
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Carcinoma/epidemiología , Carcinoma/cirugía , Gastrectomía/métodos , Recurrencia Local de Neoplasia/epidemiología , Complicaciones Posoperatorias/epidemiología , Neoplasias Gástricas/epidemiología , Neoplasias Gástricas/cirugía , Carcinoma/patología , Humanos , Neoplasias Gástricas/patología , Tasa de Supervivencia , Factores de TiempoRESUMEN
OBJECTIVE: To investigate the correlation of single nucleotide polymorphisms (SNP) of XRCC1 gene to hereditary susceptibility of colorectal cancer. METHODS: XRCC1 genotypes in 124 colorectal cancer patients and 214 matched healthy people as control were analyzed by SnaP Shot SNP-typing technique. Five different inheritance models including codominant, dominant, recessive, overdominant and log-additive were analyzed using logistic regression model. The haplotype distribution was estimated with phase and its correlation with the risk of colorectal cancer was evaluated. RESULTS: The frequencies of mutant 25487G-A, 25489C-T and 1799782C-T alleles were 0.20, 0.11, 0.32 respectively in the patients, and 0.23, 0.13, 0.34 in the controls. There was no significant correlation of polymophisms of XRCC1 gene to the risk of colorectal cancer in 5 different inheritance models (P>0.05). GCT, GCC, ACC and GTC were the most common haplotypes and the odds ratios were 1, 1.35, 0.90 and 0.84 respectively. There was no significant difference of distribution between 2 groups in haplotypes. CONCLUSION: Polymorphisms of XRCC1 gene, including rs25487, rs25489, rs1799782, are not associated with to the risk of colorectal cancer.