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Find video protocols related to scientific articles indexed in Pubmed.
Analysis of the CYP2C19 Genetic Polymorphism in Han and Uyghur patients with Cardiovascular and Cerebrovascular Diseases in the Kashi Area of Xinjiang.
Med. Sci. Monit.
PUBLISHED: 11-10-2014
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Background The aim of this study was to analyze the CYP2C19 genetic polymorphism among Han and Uyghur patients with cardiovascular and cerebrovascular diseases in the Kashi area of Xinjiang. Material and Methods We enrolled 1020 patients with cardiovascular and cerebrovascular diseases, including 220 Han subjects and 800 Uyghur subjects. We used the gene chip method to detect polymorphisms in CYP2C19. The allele frequencies of CYP2C19 and the metabolic phenotype frequencies were then compared between the 2 ethnic groups. Results The frequency of CYP2C19 *1 was 0.6454 in Han subjects and 0.7869 in Uyghur subjects, and the difference was statistically significant (P<0.05). The frequency of CYP2C19 *2 was 0.3273 in Han subjects and 0.1837 in Uyghur subjects (P<0.05). The frequency of the homozygous extensive metabolizer phenotype was 42.72% and 62.13% in Han and Uyghur subjects, respectively (P<0.01). The frequency of the heterozygous extensive metabolizer phenotype was 43.64% and 33.13% in Han and Uyghur subjects, respectively (P<0.01). The frequency of poor metabolizers in Han and Uyghur subjects was 13.64% and 4.76%, respectively (P<0.01). Conclusions Among patients with cardiovascular and cerebrovascular diseases located in the Kashgar Prefecture of Xinjiang, there is a differential distribution of CYP2C19 genotypes between the Han and Uyghur populations. Uyghur patients showed higher frequencies of extensive metabolizer genotypes than Han patients, while Han patients showed higher frequencies of poor metabolizer genotypes than Uyghur patients.
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Photoswitching of the Triplet Excited State of DiiodoBodipy-Dithienylethene Triads and Application in Photo-Controllable Triplet-Triplet Annihilation Upconversion.
J. Org. Chem.
PUBLISHED: 11-10-2014
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Dithienylethene (DTE)-2,6-diiodoBodipy triads were prepared with the aim to photoswitch the triplet excited state of the 2,6-diiodoBodipy moiety. Bodipy was selected due to its low T1 state energy level to avoid sensitized photocyclization of DTE, which is very often encountered in DTE photoswitches, so that the photochemistry of DTE and the organic chromophore can be addressed independently. This is the first time that DTE was covalently connected with an organic triplet photosensitizer. For the triad with DTE-o structure, selective photoexcitation into the diiodoBodipy part did not initiate photocyclization of DTE-o. Upon photoirradiation at 254 nm, thus the DTE-o ? DTE-c transformation, the intersystem crossing (ISC) of 2,6-diiodoBodipy moiety was competed by the photoactivated resonance energy transfer (RET), with Bodipy as the intramolecular energy donor and DTE-c as energy acceptor. The fluorescence of Bodipy was quenched and the triplet state lifetime of Bodipy was reduced from 105.1 to 40.9 ?s. The photoreversion is O2-independent, but can be greatly accelerated upon selective photoexcitation into the diiodoBodipy absorption band (at 535 nm). We concluded that ISC is not outcompeted by RET. The photoswitching of the triplet state was transduced to the singlet oxygen photosensitizing, as well as triplet-triplet annihilation upconversion.
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Switching of the triplet excited state of rhodamine-C60 dyads.
Chem. Commun. (Camb.)
PUBLISHED: 10-31-2014
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Acid-switching of the triplet excited state in rhodamine-C60 dyads was achieved. The rhodamine moiety acts as an acid-activated visible light-harvesting antenna and C60 as the singlet energy acceptor and the spin converter, and production of the triplet state was enhanced in the presence of acid.
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Switching of the Triplet Excited State of Styryl 2,6-Diiodo-Bodipy and Its Application in Acid-Activatable Singlet Oxygen Photosensitizing.
J. Org. Chem.
PUBLISHED: 10-04-2014
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IodoBodipy-styrylBodipy dyads triplet photosensitizers were prepared (B-1 and B-2) which contain acid-responsive moiety. Both compounds show broadband visible light absorption, due to the resonance energy transfer (RET) between the two different visible light-harvesting Bodipy units. The photophysical properties of the dyads were studied with steady-state and nanosecond time-resolved transient absorption spectroscopy. The production of triplet excited state is switched ON or OFF by protonation/deprotonation of the amino group in the dyads. In the neutral form, the excited state is short-lived (<10 ns) and no singlet oxygen ((1)O2) photosensitizing was observed. Upon protonation, a long-lived triplet excited state was observed (?T = 3.1 ?s) and the (1)O2 quantum yield (??) is up to 73.8%. The energy levels of the components of the dyads were changed upon protonation and this energy level tuning exerts significant influence on the triplet state property of the dyad. Acid-activated shuffling of the localization of the triplet excited state between two components of a dyad was observed. Furthermore, we observed a rare example that a chromophore giving shorter absorption wavelength is acting as the singlet energy acceptor in RET. The experimental results were rationalized by density functional theory (DFT) and time-dependent DFT (TDDFT) calculations.
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2-(2-Hydroxyphenyl)-benzothiazole (HBT)-Rhodamine Dyad: Acid-Switchable Absorption and Fluorescence of Excited-State Intramolecular Proton Transfer (ESIPT).
J Phys Chem B
PUBLISHED: 09-11-2014
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Dyad was prepared by link rhodamine and excited state intramolecular proton transfer (ESIPT) chromophore 2-(2-hydroxyphenyl)-benzothiazole (HBT) using Click reaction, with the goal to switch the absorption/emission property of ESIPT chromophore. The photophysical properties of the dyad were studied with steady state and time-resolved absorption and emission spectroscopy. In the absence of acid, that is, with rhodamine is in spirolactam structure, ESIPT was observed, the enol form emission of HBT unit was observed at 404 nm in protic solvents. In aprotic solvents, emission of the keto form of HBT was observed at 543 nm. With addition of acid such as trifluoroacetic acid, the rhodamine unit transforms to the opened amide structure, intense absorption band at 554 nm developed, as well as a strong fluorescence band at 579 nm; in EtOH, the enol emission of HBT at 406 nm was not quenched by the resonance energy transfer (RET), thus, dual fluorescence was observed. In dichloromethane, however, the fluorescence of the keto form of HBT unit was completely quenched. Thus, the absorption and emission of the ESIPT chromophore were switched by a acid/base-activatable rhodamine chromophore. Such studies will add additional modulability to the ESIPT chromophores.
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Core-binding factor subunit beta is not required for non-primate lentiviral Vif-mediated APOBEC3 degradation.
J. Virol.
PUBLISHED: 08-13-2014
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Viral infectivity factor (Vif) is required for lentivirus fitness and pathogenicity, except in equine infectious anemia virus (EIAV). Vif enhances viral infectivity by a Cullin5-Elongin B/C E3 complex to inactivate the host restriction factor APOBEC3. Core-binding factor subunit beta (CBF-?) is a cell factor that was recently shown to be important for the primate lentiviral Vif function. Non-primate lentiviral Vif also degrades APOBEC3 through the proteasome pathway. However, it is unclear whether CBF-? is required for the non-primate lentiviral Vif function. In this study, we demonstrated that the Vifs of non-primate lentiviruses, including feline immunodeficiency virus (FIV), bovine immunodeficiency virus (BIV), caprine arthritis encephalitis virus (CAEV), and maedi-visna virus (MVV), do not interact with CBF-?. In addition, CBF-? did not promote the stability of FIV, BIV, CAEV, and MVV Vifs. Furthermore, CBF-? silencing or overexpression did not affect non-primate lentiviral Vif-mediated APOBEC3 degradation. Our results suggest that non-primate lentiviral Vif induces APOBEC3 degradation through a different mechanism than primate lentiviral Vif. Importance: The APOBEC3 protein family members are host restriction factors that block retrovirus replication. Vif, an accessory protein of lentivirus, degrades APOBEC3 to rescue viral infectivity by forming Cullin5-Elongin B/C-based E3 complex. CBF-? was proved to be a novel regulator of primate lentiviral Vif function. In this study, we found that CBF-? knockdown or overexpression did not affect FIV Vif's function, which induced polyubiquitination and degradation of APOBEC3 by recruiting the E3 complex in a manner similar to that of HIV-1 Vif. We also showed that other non-primate lentiviral Vifs did not require CBF-? to degrade APOBEC3. CBF-? did not interact with non-primate lentiviral Vifs or promote their stability. These results suggest that a different mechanism exists for the Vif-APOBEC interaction and that non-primates are not suitable animal models for exploring pharmacological interventions that disrupt Vif-CBF-? interaction.
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The effect of the regioisomeric naphthalimide acetylide ligands on the photophysical properties of N^N Pt(II) bisacetylide complexes.
Dalton Trans
PUBLISHED: 08-01-2014
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Two N^N Pt(II) bis(acetylide) complexes Pt-1 and Pt-2 with regioisomeric amino NI acetylide ligands (L-1 and L-2, L-1 = 5-amino-4-ethylnaphthaleneimide; L-2 = 3-amino-4-ethylnaphthaleneimide) were prepared. The photophysical properties of the complexes were studied by steady state and time-resolved spectroscopy. The two complexes with regioisomeric ligands (Pt-1 and Pt-2) show different photophysical properties such as maximal absorption wavelength (485 nm vs. 465 nm), triplet excited state lifetimes (23.7 ?s vs. 0.9 ?s), and different solvent-polarity dependences of the emission properties. The absorption of the complexes is red-shifted as compared with the previously reported Pt(II) complex containing the 4-ethylnaphthaleneimide ligand. The two complexes with regioisomeric NI ligands were used as triplet photosensitizers for triplet-triplet annihilation (TTA) upconversion; drastically different upconversion quantum yields (15.0% vs. 1.1%) were observed. Our results are useful for designing new visible light-harvesting Pt(II) bisacetylide complexes as triplet photosensitizers which can be used in areas such as photocatalysis, photodynamic therapy and TTA upconversion.
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Prevalence, Awareness, Treatment and Control of Hypertension in Macau: Results From a Cross-Sectional Epidemiological Study in Macau, China.
Am. J. Hypertens.
PUBLISHED: 07-27-2014
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Awareness of hypertension, as well as its prevalence, treatment, and control status, has not been comprehensively investigated in Macau Special Administrative Region (SAR), China.
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Phylogenetic analysis of a novel H6N6 avian influenza virus isolated from a green peafowl in China and its pathogenic potential in mice.
Infect. Genet. Evol.
PUBLISHED: 07-03-2014
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To explore the ecology of the H6 subtype avian influenza viruses in Hebei Province, China, a long-term surveillance was conducted in 2012 among domestic poultry and birds in a wildlife park. In this study, we report the characterization of a novel H6N6 avian influenza virus isolated from a healthy green peafowl in Qinghuangdao Wildlife Park in 2012. A phylogenetic analysis indicated that the isolated H6N6 strain has the same gene constellation as the ST3367-like strains, which are mainly distributed in southern and eastern China. A mouse experiment showed that the isolate replicated efficiently in the lungs and turbinates of infected mice without previous adaptation, resulting in locally thickened alveolar septa and interstitial pneumonia. Further studies of the H6 subtype viruses are required to clarify their evolutionary pattern in north China, which will benefit disease control and pandemic preparedness for novel viruses.
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Discovery of novel non-ATP competitive FGFR1 inhibitors and evaluation of their anti-tumor activity in non-small cell lung cancer in vitro and in vivo.
Oncotarget
PUBLISHED: 07-02-2014
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Accumulating evidence suggests that high expression of FGFR1 is closely related to the development of lung cancer especially in non-small cell lung cancers (NSCLC), to which non-ATP competitive inhibitors represent an effective therapeutical approach due to their good specificity. Herein, a series of NDGA analogues with the framework of bisaryl-1,4-dien-3-one as novel FGFR1 inhibitors have been designed and screened. Among them Aea4 and Aea25 showed strong FGFR1`inhibition and high selectivity over other receptor kinases. The kinase inhibitory assay in different ATP concentrations and computer-assistant molecular docking showed that the FGFR1 inhibition mode of both Aea4 and Aea25 was non-ATP-competitive. The in vitro and in vivo study on anticancer efficacy of Aea4 and Aea25 against non-small cell lung cancer involves inhibition of cell proliferation, apoptosis induction and cell cycle arrest with no toxicity. Thus, these two novel non-ATP competitive inhibitors derived from NDGA may have a great therapeutic potential in the treatment of NSCLC. This work also provides a structural lead for the design of new non-ATP-competitive FGFR1 inhibitors.
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Reversible photoswitching of triplet-triplet annihilation upconversion using dithienylethene photochromic switches.
J. Am. Chem. Soc.
PUBLISHED: 06-24-2014
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Reversible photoswitched triplet-triplet annihilation upconversion (TTA UC) was demonstrated with dithienylethene (DTE) derivatives as the photochromic units, 2,6-diiodoBodipy as the triplet photosensitizer, and perylene as the triplet acceptor/emitter. The TTA UC is undisturbed by the open-form DTE but can be switched OFF upon photoirradiation of the mixture of the three components at 254 nm, i.e., by the closed-form DTE. Subsequent visible light irradiation restores the TTA UC. By studying the competitive triplet-state energy-transfer processes with nanosecond time-resolved transient difference absorption and fluorescence spectroscopy, we confirmed that the quenching of the perylene triplet excited state by closed-form DTE is dominant among the four possible quenching processes.
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Broadband Visible-Light-Harvesting trans-Bis(alkylphosphine) Platinum(II)-Alkynyl Complexes with Singlet Energy Transfer between BODIPY and Naphthalene Diimide Ligands.
Chemistry
PUBLISHED: 06-02-2014
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A heteroleptic bis(tributylphosphine) platinum(II)-alkynyl complex (Pt-1) showing broadband visible-light absorption was prepared. Two different visible-light-absorbing ligands, that is, ethynylated boron-dipyrromethene (BODIPY) and a functionalized naphthalene diimide (NDI) were used in the molecule. Two reference complexes, Pt-2 and Pt-3, which contain only the NDI or BODIPY ligand, respectively, were also prepared. The coordinated BODIPY ligand shows absorption at 503?nm and fluorescence at 516?nm, whereas the coordinated NDI ligand absorbs at 594?nm; the spectral overlap between the two ligands ensures intramolecular resonance energy transfer in Pt-1, with BODIPY as the singlet energy donor and NDI as the energy acceptor. The complex shows strong absorption in the region 450?nm-640?nm, with molar absorption coefficient up to 88?000?M(-1) ?cm(-1) . Long-lived triplet excited states lifetimes were observed for Pt-1-Pt-3 (36.9??s, 28.3??s, and 818.6??s, respectively). Singlet and triplet energy transfer processes were studied by the fluorescence/phosphorescence excitation spectra, steady-state and time-resolved UV/Vis absorption and luminescence spectra, as well as nanosecond time-resolved transient difference absorption spectra. A triplet-state equilibrium was observed for Pt-1. The complexes were used as triplet photosensitizers for triplet-triplet annihilation upconversion, with upconversion quantum yields up to 18.4?% being observed for Pt-1.
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A remarkable effect of N,N-diethylamino functionality on the optoelectronic properties of a salicylimine-based probe for Al(3+).
Dalton Trans
PUBLISHED: 04-30-2014
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A new live-cell permeable, fluorescent probe comprised of a simple salicylimine-based Schiff base (SA1) has been developed for Al3+ with nano-molar sensitivity in aqueous media. SA1 was synthesized through a simple structural modification of a recently reported receptor SA2 by the incorporation of the N,Ndiethylamino (DEA) group as a fine controllable unit. This modification affects the performance of SA1 remarkably in terms of its sensitivity, water compatibility and efficiency as well as its mechanistic aspect. The presence of the DEA group in SA1 led to its dual channel emission due to the TICT state and at the same time its hydrophobic nature was also responsible for controlling the strong hydration of Al3+ ions in aqueous media which ultimately led to the high sensitivity of SA1 for Al3+. The structure of SA1 was confirmed by single crystal X-ray diffraction and its binding with Al3+ was studied in detail using UVvisible, fluorescence and 1H NMR spectral studies along with mass determination. The effort of getting a single crystal of Al3+–SA1 led to single crystals of Cl?/NO3 ? complexes of protonated SA1 which were fully characterized by their XRD studies.
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A novel FGF2 antagonist peptide P8 with potent antiproliferation activity.
Tumour Biol.
PUBLISHED: 04-29-2014
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Some fibroblast growth factors (FGFs) play a critical role in tumorigenesis and progression. Among them, FGF2 was highly expressed in some tumors, and antagonists binding to FGF2 can suppress the growth of tumor cells. Therefore, FGF2 has been considered as an important target in cancer therapy. In this study, we identified a novel FGF2-binding short peptide (P8, PLLQATAGGGS-NH2) using phage display technology and alanine scanning. The P8 peptide suppressed FGF2-induced proliferation with no cytotoxic effect on cells, arrested the cycle at the G0/G1 phase in B16-F10 cells, and downregulated the activation of fibroblast growth factor receptor substrate 2? (FRS2?)/ERK cascade in B16-F10, NIH-H460, and SGC-7901 cells. Besides, P8 peptide can also inhibit the phosphorylation of FRS2? stimulated by FGF1 and KGF2. These implied that P8 peptide may develop as a multi-target antagonist peptide contributing to tumor treatment.
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Synthesis and evaluation of a series of novel asymmetrical curcumin analogs for the treatment of inflammation.
Molecules
PUBLISHED: 04-12-2014
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Curcumin has been reported to possess multiple bioactivities, such as antioxidant, anticancer, and anti-inflammatory properties, however the clinical application of curcumin has been significantly limited by its instability and poor metabolism. Modification of curcumin has led to discovery and development of lots of novel therapeutic candidates. In recent years acute and chronic inflammation has been the focus of numerous studies in various diseases. Here, we synthesized a series of asymmetrical curcumin analogs with high in vitro chemical stability, and their anti-inflammatory activity was evaluated in LPS-stimulated macrophages. According to the bio-screening results and QSAR analysis, these analogs exhibited potent activities against LPS-induced TNF-? and IL-6 release. Among the analogs of the potent anti-inflammatory activity, compounds 3b8 and 3b9 exhibited significant protection and possess enhanced anti-inflammatory activity thereby attenuated the LPS-induced septic death in mice.
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Molecular engineering of simple phenothiazine-based dyes to modulate dye aggregation, charge recombination, and dye regeneration in highly efficient dye-sensitized solar cells.
Chemistry
PUBLISHED: 04-08-2014
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A series of simple phenothiazine-based dyes, namely, TP, EP, TTP, ETP, and EEP have been developed, in which the thiophene (T), ethylenedioxythiophene (E), their dimers, and mixtures are present to modulate dye aggregation, charge recombination, and dye regeneration for highly efficient dye-sensitized solar cell (DSSC) applications. Devices sensitized by the dyes TP and TTP display high power conversion efficiencies (PCEs) of 8.07 (Jsc = 15.2?mA?cm(-2), Voc =0.783?V, fill factor (FF) = 0.679) and 7.87?% (Jsc = 16.1?mA?cm(-2), Voc = 0.717?V, FF = 0.681), respectively; these were measured under simulated AM 1.5 sunlight in conjunction with the I(-)/I3(-) redox couple. By replacing the T group with the E unit, EP-based DSSCs had a slightly lower PCE of 7.98?% with a higher short-circuit photocurrent (Jsc) of 16.7?mA?cm(-2). The dye ETP, with a mixture of E and T, had an even lower PCE of 5.62?%. Specifically, the cell based on the dye EEP, with a dimer of E, had inferior Jsc and Voc values and corresponded to the lowest PCE of 2.24?%. The results indicate that the photovoltaic performance can be finely modulated through structural engineering of the dyes. The selection of T analogues as donors can not only modulate light absorption and energy levels, but also have an impact on dye aggregation and interfacial charge recombination of electrons at the interface of titania, electrolytes, and/or oxidized dye molecules; this was demonstrated through DFT calculations, electrochemical impedance analysis, and transient photovoltage studies.
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Feasibility of using a dual-promoter recombinant baculovirus vector to coexpress EGFP and GDNF in mammalian cells.
Exp Ther Med
PUBLISHED: 03-18-2014
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Vectors that are capable of coexpressing two or more exogenous genes for in vitro and in vivo gene delivery are being increasingly studied. The aim of the present study was to explore the feasibility of using the pFastBac™ Dual vector, under the control of two cytomegalovirus (CMV) promoters with opposite directions, to coexpress enhanced green fluorescent protein (EGFP) and glial cell line-derived neurotrophic factor (GDNF) in the same mammalian cell. In the study, two promoters in the pFastBac Dual vector were replaced with CMV-EGFP and CMV-GDNF, whose directions were consistent with the initial directions. The pFastBac Dual-CMV-EGFP-CMV-GDNF plasmid was constructed and then transfected into human embryonic kidney (HEK) 293T cells. The recombinant virus, Bac Dual-CMV-EGFP-CMV-GDNF, was generated with the Bac-to-Bac Baculovirus Expression system and used to transduce HeLa cells. Immunofluorescence was applied to examine the coexpression of EGFP and GDNF in transfected or transduced mammalian cells, while western blot analysis was used to confirm the expression of GDNF in transduced HeLa cells. The recombinant plasmid was constructed and the recombinant baculovirus was successfully generated. Immunofluorescence observations demonstrated that EGFP and GDNF were simultaneously expressed in the same transfected HEK 293T cell and in a single transduced HeLa cell. Western blot analysis revealed that GDNF was expressed accurately in the transduced cells. Therefore, the pFastBac Dual vector is an efficient gene transfer vector that is able to coexpress two target proteins in mammalian cells and serve as a platform for combining reporter or/and therapy genes used in molecular imaging and dual-gene therapy. Thus, the current study presents a new coexpression strategy for dual-gene delivery in vitro and in vivo.
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Construction and analysis of Siberian tiger bacterial artificial chromosome library with approximately 6.5-fold genome equivalent coverage.
Int J Mol Sci
PUBLISHED: 03-11-2014
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Bacterial artificial chromosome (BAC) libraries are extremely valuable for the genome-wide genetic dissection of complex organisms. The Siberian tiger, one of the most well-known wild primitive carnivores in China, is an endangered animal. In order to promote research on its genome, a high-redundancy BAC library of the Siberian tiger was constructed and characterized. The library is divided into two sub-libraries prepared from blood cells and two sub-libraries prepared from fibroblasts. This BAC library contains 153,600 individually archived clones; for PCR-based screening of the library, BACs were placed into 40 superpools of 10 × 384-deep well microplates. The average insert size of BAC clones was estimated to be 116.5 kb, representing approximately 6.46 genome equivalents of the haploid genome and affording a 98.86% statistical probability of obtaining at least one clone containing a unique DNA sequence. Screening the library with 19 microsatellite markers and a SRY sequence revealed that each of these markers were present in the library; the average number of positive clones per marker was 6.74 (range 2 to 12), consistent with 6.46 coverage of the tiger genome. Additionally, we identified 72 microsatellite markers that could potentially be used as genetic markers. This BAC library will serve as a valuable resource for physical mapping, comparative genomic study and large-scale genome sequencing in the tiger.
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Perylene-derived triplet acceptors with optimized excited state energy levels for triplet-triplet annihilation assisted upconversion.
J. Org. Chem.
PUBLISHED: 02-21-2014
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A series of perylene derivatives are prepared as triplet energy acceptors for triplet-triplet annihilation (TTA) assisted upconversion. The aim is to optimize the energy levels of the T1 and S1 states of the triplet acceptors, so that the prerequisite for TTA (2E(T1) > E(S1)) can be better satisfied, and eventually to increase the upconversion efficiency. Tuning of the energy levels of the excited states of the triplet acceptors is realized either by attaching aryl groups to perylene (via single or triple carbon-carbon bonds), or by assembling a perylene-BODIPY dyad, in which the components present complementary S1 and T1 state energy levels. The S1 state energy levels of the perylene derivatives are generally decreased compared to perylene. The anti-Stokes shift, TTA, and upconversion efficiencies of the new triplet acceptors are improved with respect to the perylene hallmark. For the perylene-BODIPY dyads, the fluorescence emission was substantially quenched in polar solvents. Moreover, we found that extension of the ?-conjugation of BODIPY energy donor significantly reduces the energy level of the S1 state. Low S1 state energy level and high T1 state energy level are beneficial for triplet photosensitizers.
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Preclinical evaluation of recombinant human IFN?2b-containing magnetoliposomes for treating hepatocellular carcinoma.
Int J Nanomedicine
PUBLISHED: 01-01-2014
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Magnetoliposomes are phospholipid vesicles encapsulating magnetic nanoparticles that can be used to encapsulate therapeutic drugs for delivery into specific organs. Herein, we developed magnetoliposomes containing recombinant human IFN?2b, designated as MIL, and evaluated this combination's biological safety and therapeutic effect on both cellular and animal hepatocellular carcinoma models. Our data showed that MIL neither hemolyzed erythrocytes nor affected platelet-aggregation rates in blood. Nitroblue tetrazolium-reducing testing showed that MIL did not change the absolute numbers or phagocytic activities of leukocytes. Acute-toxicity testing also showed that MIL had no devastating effect on mice behaviors. All the results indicated that the nanoparticles could be a safe biomaterial. Pharmacokinetic analysis and tissue-distribution studies showed that MIL maintained stable and sustained drug concentrations in target organs under a magnetic field, helped to increase bioavailability, and reduced administration time. MIL also dramatically inhibited the growth of hepatoma cells. Targeting of MIL in the livers of nude mice bearing human hepatocellular carcinoma showed that MIL significantly reduced the tumor size to 38% of that of the control group. Further studies proved that growth inhibition of cells or tumors was due to apoptosis-signaling pathway activation by human IFN?2b.
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Merocel versus Nasopore for nasal packing: a meta-analysis of randomized controlled trials.
PLoS ONE
PUBLISHED: 01-01-2014
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To compare the clinical outcomes, including efficacy and complications, of Merocel versus Nasopore as a nasal packing material after nasal surgery.
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Synthesis of BiOI-TiO2 composite nanoparticles by microemulsion method and study on their photocatalytic activities.
ScientificWorldJournal
PUBLISHED: 01-01-2014
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This study was conducted to synthesize a series of nanosized BiOI-TiO2 catalysts to photodegrade Bisphenol A solution. The BiOI-TiO2 nanoparticles were synthesized in the reverse microemulsions, consisting of cyclohexane, Triton X-100, n-hexanol, and aqueous salt solutions. The synthesized particles were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) surface analyzer, Fourier transform-infrared spectroscopy (FT-IR), ultraviolet-visible light (UV-Vis) absorption spectra and transmission electron microscope (TEM). The photodegradation of Bisphenol A (BPA) in aqueous suspension under visible light irradiation was investigated to explore the feasibility of using the photocatalytic method to treat BPA wastewater. The effects of different molar ratios of BiOI to TiO2 on the photocatalytic activity were discussed. The experimental results revealed that the photocatalytic effect of the BiOI-TiO2 particles was superior to the commercial P25 TiO2. The BPA degradation could be approached by a pseudo-first-order rate expression. The observed reaction rate constant (kobs) was related to nanoparticles dosage and initial solution pH.
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Facile preparation and characterization of BiOI-rectorite composite with high adsorptive capacity and photocatalytic activity.
Dalton Trans
PUBLISHED: 12-10-2013
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Rectorite was composited with BiOI to extend its applicability as an applied material with high adsorptive capacity and photocatalytic activity. The facile synthesis process involved ultrasonic irradiation and in situ reaction. The physicochemical properties of the as-prepared samples were characterized by means of X-ray diffraction (XRD), Fourier transform-infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), N2 adsorption-desorption isotherms, and UV-vis diffuse reflectance spectroscopy (UV-vis DRS). Rhodamine B (RhB), a typical organic contaminant, was used as the model contaminant to evaluate the adsorption capacity and photocatalytic performance of the prepared BiOI-rectorite composite. The adsorption process was found to obey pseudo-second-order kinetics. The equilibrium adsorption was well-modeled using the Freundlich adsorption isotherm. High photocatalytic activity under visible light irradiation was observed.
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Identification of a novel peptide that blocks basic fibroblast growth factor-mediated cell proliferation.
Oncotarget
PUBLISHED: 10-22-2013
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Basic fibroblast growth factor (bFGF) has been implicated in tumor growth via interactions with its receptors (FGFRs) on the cell surface and therefore, bFGF/FGFRs are considered essential targets for cancer therapy. Herein, a consensus heptapeptide (LSPPRYP) was identified for the first time from a phage display heptapeptide library after three sequential rounds of biopanning against FGFR-expressing cells with competitive displacement of phage by bFGF, followed by subtraction of non-specific binding by FGFR-deficient cells. Phage bearing LSPPRYP showed high levels of binding to Balb/c 3T3 cells expressing high-affinity bFGF-binding FGFR (bFGFR), but not to the cells that do not express bFGFR (Cos-7), or express a very low affinity bFGFR (HaCat). The selected-phage-derived peptide synthesized by solid phase method using a rapid and practical Fmoc strategy was found to specifically compete with bFGF for binding to its receptors, inhibit bFGF-stimulated cell proliferation by inducing cell cycle arrest, and block bFGF-induced activation of Erk1 and Erk2 kinase in B16-F10 melanoma cells. Importantly, treatment of melanoma-bearing mice with the synthetic peptide significantly suppressed tumor growth. The results demonstrate a strong anticancer activity of the isolated bFGFR-binding peptide (and its future derivatives), which may have great potential for cancer therapy.
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Zinc(II) tetraphenyltetrabenzoporphyrin complex as triplet photosensitizer for triplet-triplet annihilation upconversion.
Chem. Commun. (Camb.)
PUBLISHED: 09-09-2013
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Zn(II) tetraphenyltetrabenzoporphyrin (TPTBP) and the free base H2TPTBP were used as triplet photosensitizers for triplet-triplet annihilation (TTA) upconversion, to replace the long-established precious metal complex triplet photosensitizers such as those containing Pd(II)-Pt(II) atoms.
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Red-light-absorbing diimine Pt(II) bisacetylide complexes showing near-IR phosphorescence and long-lived 3IL excited state of Bodipy for application in triplet-triplet annihilation upconversion.
Dalton Trans
PUBLISHED: 09-07-2013
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Bodipy is used for the preparation of Pt(II) bisacetylide complexes which show strong absorption of visible light and long-lived triplet state. Room temperature (RT) near-IR phosphorescence of Bodipy was observed. The ?-conjugation framework of visible light-harvesting Bodipy ligand was connected to the Pt(II) center by the C?C bond. The complexes were used as triplet photosensitizers for triplet-triplet annihilation (TTA) upconversion.
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Microchemostat array with small-volume fraction replenishment for steady-state microbial culture.
Lab Chip
PUBLISHED: 08-29-2013
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A chemostat is a bioreactor in which microorganisms can be cultured at steady-state by controlling the rate of culture medium inflow and waste outflow, thus maintaining media composition over time. Even though many microbial studies could greatly benefit from studying microbes in steady-state conditions, high instrument cost, complexity, and large reagent consumption hamper the routine use of chemostats. Microfluidic-based chemostats (i.e. microchemostats) can operate with significantly smaller reagent consumption while providing accurate chemostatic conditions at orders of magnitude lower cost compared to conventional chemostats. Also, microchemostats have the potential to significantly increase the throughput by integrating arrays of microchemostats. We present a microchemostat array with a unique two-depth culture chamber design that enables small-volume fraction replenishment of culture medium as low as 1% per replenishment cycle in a 250 nl volume. A system having an array of 8 microchemostats on a 40 × 60 mm(2) footprint could be automatically operated in parallel by a single controller unit as a demonstration for potential high throughput microbial studies. The model organism, Saccharomyces cerevisiae, successfully reached a stable steady-state of different cell densities as a demonstration of the chemostatic functionality by programming the dilution rates. Chemostatic functionality of the system was further confirmed by quantifying the budding index as a function of dilution rate, a strong indicator of growth-dependent cell division. In addition, the small-volume fraction replenishment feature minimized the cell density fluctuation during the culture. The developed system provides a robust, low-cost, and higher throughput solution to furthering studies in microbial physiology.
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Hetero Bodipy-dimers as heavy atom-free triplet photosensitizers showing a long-lived triplet excited state for triplet-triplet annihilation upconversion.
Chem. Commun. (Camb.)
PUBLISHED: 08-24-2013
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Bodipy dimers in which the two different sub-units take an orthogonal orientation were prepared, which show strong absorption of visible light, long-lived triplet excited states (140.9 ?s) and high singlet oxygen ((1)O2) quantum yields (64%). The dimers were used for triplet-triplet annihilation upconversion (quantum yield is up to 3.7%).
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Porous material-immobilized iodo-Bodipy as an efficient photocatalyst for photoredox catalytic organic reaction to prepare pyrrolo[2,1-a]isoquinoline.
Chem. Commun. (Camb.)
PUBLISHED: 08-17-2013
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Iodo-Bodipy immobilized on porous silica was used as an efficient recyclable photocatalyst for photoredox catalytic tandem oxidation-[3+2] cycloaddition reactions of tetrahydroisoquinoline with N-phenylmaleimides to prepare pyrrolo[2,1-a]isoquinoline.
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Modifiable risk factors including sunlight exposure and fish consumption are associated with risk of hypertension in a large representative population from Macau.
J. Steroid Biochem. Mol. Biol.
PUBLISHED: 08-03-2013
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Chinese populations are known to be at risk for vitamin D deficiency, with some evidence that this is due to lack of exposure to sunlight. Vitamin D deficiency and/or low sun exposure have been associated with higher incidence of hypertension in Caucasians. Thus, we investigated these associations in a Chinese population with a high rate of hypertension. From a random household survey of 1410 residents aged ?18 years, height, weight and blood pressure were measured and demographic, exercise and dietary data were collected, as well as estimated hours of sunlight exposure on weekdays and weekends (in winter and summer). Modifiable predictors of hypertension in these data were lack of sunlight exposure and low intake of fish as well as smoking, obesity and lack of exercise. When investigated in a linear model, sunlight exposure was negatively associated with hypertension (?=-0.072, p<0.001) as was physical activity (?=-0.021, p<0.001) and fish consumption (?=-0.177, p<0.001). In contrast body mass index (weight/height(2)) was positively associated with hypertension (?=+0.62, p<0.001), as were pack-years of smoking (?=+0.27, p<0.001). On multivariate categorical analysis taking into account demographic risk factors in these data (age, gender and occupation) having more than half an hours sun exposure per day compared to none was associated with less hypertension (OR=0.6, 95% CI: 0.4-0.8). Similarly, consuming either oily fish or seafood more than four times per week compared to less was also associated with less hypertension (oily fish (OR=0.4, 95% CI: 0.3-0.5); seafood consumption (OR=0.8, 95% CI: 0.7-0.9)). Having daily moderate physical activity compared to none was also associated with a lower risk of hypertension (OR=0.8, 95% CI: 0.7-0.9). In contrast, being obese compared to normal weight and having more than five pack-years of smoking compared to none were associated with a higher risk of hypertension (OR=4.6, 95% CI: 3.7-5.7; OR=1.4, 95% CI: 1.0-1.8, respectively). The major new findings of this study are that more sun exposure and high weekly fish consumption (especially oily fish) may be potentially modifiable independent factors for protecting against risk of hypertension in this population. This article is part of a Special Issue entitled 16th Vitamin D Workshop.
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Intramolecular RET enhanced visible light-absorbing bodipy organic triplet photosensitizers and application in photooxidation and triplet-triplet annihilation upconversion.
J. Am. Chem. Soc.
PUBLISHED: 07-08-2013
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Resonance energy transfer (RET) was used for the first time to enhance the visible light absorption of triplet photosensitizers. The intramolecular energy donor (boron-dipyrromethene, Bodipy) and acceptor (iodo-Bodipy) show different absorption bands in visible region, thus the visible absorption was enhanced as compared to the monochromophore triplet photosensitizers (e.g., iodo-Bodipy). Fluorescence quenching and excitation spectra indicate that the singlet energy transfer is efficient for the dyad triplet photosensitizers. Nanosecond time-resolved transient absorption spectroscopy has confirmed that the triplet excited states of the dyads are distributed on both the energy donor and acceptor, which is the result of forward singlet energy transfer from the energy donor to the energy acceptor and in turn the backward triplet energy transfer. This ping-pong energy transfer was never reported for organic molecular arrays, and so it is useful to study the energy level of organic chromophores. The triplet photosensitizers were used for singlet oxygen ((1)O2) mediated photooxidation of 1,5-dihydroxylnaphthalene to produce juglone. The visible light absorption of the new visible light-absorbing triplet photosensitizers are higher than the conventional monochromophore based triplet photosensitizers, as a result, the (1)O2 photosensitizing ability is improved with the new triplet photosensitizers. Triplet-triplet annihilation upconversion with these triplet photosensitizers was also studied. Our results are useful to design the triplet photosensitizers showing strong visible light absorbance and for their applications in photocatalysis and photodynamic therapy.
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Energy-funneling-based broadband visible-light-absorbing bodipy-c60 triads and tetrads as dual functional heavy-atom-free organic triplet photosensitizers for photocatalytic organic reactions.
Chemistry
PUBLISHED: 06-27-2013
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C60 -bodipy triads and tetrads based on the energy-funneling effect that show broadband absorption in the visible region have been prepared as novel triplet photosensitizers. The new photosensitizers contain two or three different light-harvesting antennae associated with different absorption wavelengths, resulting in a broad absorption band (450-650?nm). The panchromatic excitation energy harvested by the bodipy moieties is funneled into a spin converter (C60 ), thus ensuring intersystem crossing and population of the triplet state. Nanosecond time-resolved transient absorption and spin density analysis indicated that the T1 state is localized on either C60 or the antennae, depending on the T1 energy levels of the two entities. The antenna-localized T1 state shows a longer lifetime (?T =132.9??s) than the C60 -localized T1 state (ca. 27.4??s). We found that the C60 triads and tetrads can be used as dual functional photocatalysts, that is, singlet oxygen ((1) O2 ) and superoxide radical anion (O2 (.) (-) ) photosensitizers. In the photooxidation of naphthol to juglone, the (1) O2 photosensitizing ability of the C60 triad is a factor of 8.9 greater than the conventional triplet photosensitizers tetraphenylporphyrin and methylene blue. The C60 dyads and triads were also used as photocatalysts for O2 (.) (-) -mediated aerobic oxidation of aromatic boronic acids to produce phenols. The reaction times were greatly reduced compared with when [Ru(bpy)3 Cl2 ] was used as photocatalyst. Our study of triplet photosensitizers has shown that broadband absorption in the visible spectral region and long-lived triplet excited states can be useful for the design of new heavy-atom-free organic triplet photosensitizers and for the application of these triplet photosensitizers in photo-organocatalysis.
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Visible light-absorbing rhenium(I) tricarbonyl complexes as triplet photosensitizers in photooxidation and triplet-triplet annihilation upconversion.
Dalton Trans
PUBLISHED: 06-25-2013
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We prepared N^N Re(I) tricarbonyl chloride complexes (Re-1 and Re-2) that give very strong absorption of visible light. To this end, it is for the first time that boron dipyrimethane (Bodipy) was used to prepare Re(I) tricarbonyl chloride complexes. The ?-conjugation linker between the ?-conjugation framework of the antenna Bodipy and the Re(I) coordination centre ensures efficient intersystem crossing (ISC). Re-0 without visible light-harvesting ligand was prepared as a model complex in the photophysical studies. Re-1 (with Bodipy) and Re-2 (with carbazole-ethynyl Bodipy) show unprecedented strong absorption of visible light at 536 nm (? = 91700 M(?1) cm(?1)) and 574 nm (? = 64,600 M(?1) cm(?1)), respectively. Interestingly, different from Re-0, Re-1 and Re-2 show fluorescence of the ligand, not the phosphorescence of the Re(I) coordination centre. However, long-lived triplet excited states were observed upon visible light excitation (?(T) = 104.0 ?s for Re-1; ?(T) = 127.2 ?s for Re-2) vs. the short lifetime of Re-0 (?(T) = 26 ns). With nanosecond time-resolved transient absorption spectroscopy and DFT calculations, we proved that the triplet excited states of Re-1 and Re-2 are localized on the Bodipy ligands. The complexes were used as triplet photosensitizers for two triplet–triplet-energy-transfer (TTET) processes, i.e.(1)O(2) mediated photooxidation and triplet–triplet annihilation (TTA) upconversion. With the strong visible light-harvesting ability, Re-1 proved to be a better (1)O(2) photosensitizer than the conventional triplet photosensitizer tetraphenylporphyrin (TPP). Significant upconversion was observed with Re-1 as the triplet photosensitizer. Our result is useful for preparation of Re(I) tricarbonyl chloride complexes that show strong absorption of visible light and long-lived triplet excited states and for the application of these complexes as triplet photosensitizers in photocatalysis, photodynamic therapy and TTA upconversion.
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Bodipy derivatives as organic triplet photosensitizers for aerobic photoorganocatalytic oxidative coupling of amines and photooxidation of dihydroxylnaphthalenes.
J. Org. Chem.
PUBLISHED: 05-23-2013
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We used iodo-Bodipy derivatives that show strong absorption of visible light and long-lived triplet excited states as organic catalysts for photoredox catalytic organic reactions. Conventionally most of the photocatalysts are based on the off-the-shelf compounds, usually showing weak absorption in the visible region and short triplet excited state lifetimes. Herein, the organic catalysts are used for two photocatalyzed reactions mediated by singlet oxygen ((1)O2), that is, the aerobic oxidative coupling of amines and the photooxidation of dihydroxylnaphthalenes, which is coupled to the subsequent addition of amines to the naphthoquinones, via C-H functionalization of 1,4-naphthoquinone, to produce N-aryl-2-amino-1,4-naphthoquinones (one-pot reaction), which are anticancer and antibiotic reagents. The photoreactions were substantially accelerated with these new iodo-Bodipy organic photocatalysts compared to that catalyzed with the conventional Ru(II)/Ir(III) complexes, which show weak absorption in the visible region and short-lived triplet excited states. Our results will inspire the design and application of new organic triplet photosensitizers that show strong absorption of visible light and long-lived triplet excited state and the application of these catalysts in photoredox catalytic organic reactions.
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Observation of the long-lived triplet excited state of perylenebisimide (PBI) in C^N cyclometalated Ir(III) complexes and application in photocatalytic oxidation.
Dalton Trans
PUBLISHED: 05-15-2013
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Perylenebisimide (PBI) was used to prepare C^N cyclometalated Ir(III) complexes that show strong absorption of visible light and it is the first time the long-lived triplet excited state of PBI chromophore was observed in a transition metal complex (?T = 22.3 ?s). Previously, the lifetime of the triplet state of PBI in transition metal complexes was usually shorter than 1.0 ?s. Long-lived triplet excited states are useful for applications in photocatalysis or other photophysical processes concerning triplet-triplet-energy-transfer. PBI and amino-PBI were used for preparation of cyclometalated Ir(III) complexes (Ir-2 and Ir-3), in which the PBI chromophore was connected to the coordination center via C?C ?-conjugation bond. The new complexes show strong absorption in visible region (? = 34,200 M(-1) cm(-1) at 541 nm for Ir-2, and ? = 19,000 at 669 nm for Ir-3), compared to the model complex Ir(ppy)(bpy)[PF6] Ir-1 (? < 5000 M(-1) cm(-1) in the region beyond 400 nm). The nanosecond time-resolved transient absorption and DFT calculations indicated that PBI-localized long-lived (3)IL states were populated for Ir-2 and Ir-3 upon photoexcitation. The complexes were used as triplet photosensitizers for (1)O2-mediated photooxidation of 1,5-dihydronaphthalene to produce juglone, an important intermediate for preparation of anti-cancer compounds. (1)O2 quantum yields (?(?)) up to 91% were observed for the new Ir(III) complexes and the overall photosensitizing ability is much higher than the conventional Ir(III) complex Ir-1, which shows the typical weak visible light absorption in visible region. Our results are useful for preparation of transition metal complexes that show strong absorption of visible light and long-lived triplet excited state and for the application of these complexes in photocatalysis.
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Visible light-harvesting trans bis(alkylphosphine) platinum(II)-alkynyl complexes showing long-lived triplet excited states as triplet photosensitizers for triplet-triplet annihilation upconversion.
Dalton Trans
PUBLISHED: 04-29-2013
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Symmetric and asymmetric linear trans-bis(tributylphosphine) Pt(II) bis(acetylide) complexes with functionalized aryl alkynyl ligands (coumarin, naphthalimide and phenyl acetylides) were prepared, which show enhanced absorption in the visible region (molar absorption coefficients up to 76,800 M(-1) cm(-1) at 459 nm) and long-lived triplet excited states (up to 139.9 ?s). At room temperature, the naphthalimide acetylide-phenyl acetylide complex (Pt-4) shows dual emission (fluorescence-phosphorescence), whereas other complexes show only fluorescence emission. The triplet excited states of the complexes were studied with nanosecond time-resolved transient difference absorption spectroscopy and DFT calculations on the spin density surface. The complexes were used as triplet photosensitizers for ratiometric O2 sensing, as well as triplet-triplet annihilation (TTA) upconversion (upconversion quantum yield up to 27.2%). The TTA upconversion of the complexes requires triplet acceptors with different T1 state energy levels and was studied with nanosecond time-resolved emission spectroscopy. Our results are useful for designing new Pt(II) complexes that show strong absorption of visible light and long-lived triplet excited states, as well as for the application of these complexes as triplet photosensitizers for O2 sensing, photocatalysis and TTA upconversion.
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Construction of a Full-Length Enriched cDNA Library and Preliminary Analysis of Expressed Sequence Tags from Bengal Tiger Panthera tigris tigris.
Int J Mol Sci
PUBLISHED: 04-24-2013
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In this study, a full-length enriched cDNA library was successfully constructed from Bengal tiger, Panthera tigris tigris, the most well-known wild Animal. Total RNA was extracted from cultured Bengal tiger fibroblasts in vitro. The titers of primary and amplified libraries were 1.28 × 106 pfu/mL and 1.56 × 109 pfu/mL respectively. The percentage of recombinants from unamplified library was 90.2% and average length of exogenous inserts was 0.98 kb. A total of 212 individual ESTs with sizes ranging from 356 to 1108 bps were then analyzed. The BLASTX score revealed that 48.1% of the sequences were classified as a strong match, 45.3% as nominal and 6.6% as a weak match. Among the ESTs with known putative function, 26.4% ESTs were found to be related to all kinds of metabolisms, 19.3% ESTs to information storage and processing, 11.3% ESTs to posttranslational modification, protein turnover, chaperones, 11.3% ESTs to transport, 9.9% ESTs to signal transducer/cell communication, 9.0% ESTs to structure protein, 3.8% ESTs to cell cycle, and only 6.6% ESTs classified as novel genes. By EST sequencing, a full-length gene coding ferritin was identified and characterized. The recombinant plasmid pET32a-TAT-Ferritin was constructed, coded for the TAT-Ferritin fusion protein with two 6× His-tags in N and C-terminal. After BCA assay, the concentration of soluble Trx-TAT-Ferritin recombinant protein was 2.32 ± 0.12 mg/mL. These results demonstrated that the reliability and representativeness of the cDNA library attained to the requirements of a standard cDNA library. This library provided a useful platform for the functional genome and transcriptome research of Bengal tigers.
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C(60)-Bodipy dyad triplet photosensitizers as organic photocatalysts for photocatalytic tandem oxidation/[3+2] cycloaddition reactions to prepare pyrrolo[2,1-a]isoquinoline.
Chem. Commun. (Camb.)
PUBLISHED: 03-27-2013
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C(60)-Bodipy hybrids exhibiting strong absorption of visible light and long-lived triplet excited states were used as photocatalysts for tandem oxidation/[3+2] cycloaddition of tetrahydroisoquinoline with N-phenylmaleimide to produce pyrrolo[2,1-a]isoquinolines. The reaction is substantially accelerated, compared to that catalyzed by Ru(bpy)(3)Cl(2).
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Green light-excitable naphthalenediimide acetylide-containing cyclometalated Ir(III) complex with long-lived triplet excited states as triplet photosensitizers for triplet-triplet annihilation upconversion.
Dalton Trans
PUBLISHED: 03-09-2013
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Naphthalenediimide (NDI) was connected to the ligand of a cyclometalated Ir(III) complex (Ir-1) via a C?C triple bond to enhance the absorption in the visible region and to access long-lived triplet excited states. Ir(ppy)2(bpy)[PF6] (Ir-2, ppy = 2-phenylpyridine and bpy = 2,2-bipyridine) was used as a model complex. The photophysical properties of the complexes were studied with steady state and time-resolved spectroscopy. Ir-1 shows strong absorption in the visible region (? = 11,000 M(-1) cm(-1) at 542 nm) and in comparison Ir-2 shows typically weak absorption in the visible region (? < 3000 M(-1) cm(-1) above 400 nm). Room temperature near IR emission at 732 nm (?(P) = 0.1%) was observed for Ir-1, which is attributed to the NDI localized emissive triplet excited state, by transient absorption spectra and DFT calculations on the spin density surface. The lifetime of the NDI-localized triplet excited state is up to 130.0 ?s, which is rarely reported for Ir(III) complexes. In comparison, Ir-2 shows phosphorescence at 578 nm and the triplet state lifetime is a typical value of 0.3 ?s. The complexes were used as triplet photosensitizers for triplet-triplet annihilation (TTA) upconversion and an upconversion quantum yield of 6.7% was observed with Ir-1. No upconversion was observed with Ir-2 as the triplet photosensitizer at the same experimental conditions.
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Preparation of ketocoumarins as heavy atom-free triplet photosensitizers for triplet-triplet annihilation upconversion.
Photochem. Photobiol. Sci.
PUBLISHED: 03-08-2013
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A series of ketocoumarin compounds were prepared as heavy atom-free triplet photosensitizers. The photophysical properties of the compounds were studied with steady state and time-resolved spectroscopy. The compounds show absorption in the visible spectral region (molar absorption coefficients are up to ? = 136,000 M(-1) cm(-1) at 448 nm) and long-lived triplet excited states (?T = 199.7 ?s) upon visible light photoexcitation. The compounds were used as triplet photosensitizers for singlet oxygen ((1)O2)-mediated photooxidation of 1,5-dihydroxylnaphthalene (DHN) to produce juglone. (1)O2 quantum yields of these compounds were determined in the range of 0.28-0.48. The ketocoumarins were also used as triplet photosensitizers for triplet-triplet annihilation (TTA) upconversion, and upconversion quantum yields up to 11.3% were observed. The results are useful for preparation of heavy atom-free triplet photosensitizers and for their application in photocatalysis and TTA upconversion.
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Triplet photosensitizers: from molecular design to applications.
Chem Soc Rev
PUBLISHED: 03-02-2013
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Triplet photosensitizers (PSs) are compounds that can be efficiently excited to the triplet excited state which subsequently act as catalysts in photochemical reactions. The name is originally derived from compounds that were used to transfer the triplet energy to other compounds that have only a small intrinsic triplet state yield. Triplet PSs are not only used for triplet energy transfer, but also for photocatalytic organic reactions, photodynamic therapy (PDT), photoinduced hydrogen production from water and triplet-triplet annihilation (TTA) upconversion. A good PS should exhibit strong absorption of the excitation light, a high yield of intersystem crossing (ISC) for efficient production of the triplet state, and a long triplet lifetime to allow for the reaction with a reactant molecule. Most transition metal complexes show efficient ISC, but small molar absorption coefficients in the visible spectral region and short-lived triplet excited states, which make them unsuitable as triplet PSs. One obstacle to the development of new triplet PSs is the difficulty in predicting the ISC of chromophores, especially of organic compounds without any heavy atoms. This review article summarizes some molecular design rationales for triplet PSs, based on the molecular structural factors that facilitate ISC. The design of transition metal complexes with large molar absorption coefficients in the visible spectral region and long-lived triplet excited states is presented. A new method of using a spin converter to construct heavy atom-free organic triplet PSs is discussed, with which ISC becomes predictable, C60 being an example. To enhance the performance of triplet PSs, energy funneling based triplet PSs are proposed, which show broadband absorption in the visible region. Applications of triplet PSs in photocatalytic organic reactions, hydrogen production, triplet-triplet annihilation upconversion and luminescent oxygen sensing are briefly introduced.
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Study on molecular imaging and radionuclide therapy of human nasopharyngeal carcinoma cells transfected with baculovirus-mediated sodium/iodine symporter gene.
Int. J. Oncol.
PUBLISHED: 02-27-2013
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The non-invasive imaging and radiotherapy by sodium/iodine symporter (NIS) gene transfer have been widely used for many experiments and some clinical studies. Baculovirus is an efficient tool for gene delivery into mammalian cells in vitro and in vivo. However, the applications of NIS and/or baculovirus in nasopharyngeal carcinoma (NPC) cells have not been reported yet. In this study, two recombinant baculoviruses expressing, respectively, NIS and green fluorescent protein (GFP), both under the control of the cytomegalovirus promoter (Bac-NIS and Bac-GFP) were successfully constructed. The infection efficiency and GFP fluorescence intensity of the human NPC cell line CNE-2Z infected by Bac-GFP at different setting of multiplicity of infection (MOI) were determined by flow cytometry. NIS protein expression was detected by indirect immunofluorescence. The 125I uptake and efflux of infected CNE-2Z cells by Bac-NIS were measured by a ?-counter. The cytotoxicity of baculovirus and sodium butyrate and inhibition of iodine uptake by NaClO4 were examined. The radioactivity and GFP fluorescence intensity in co-infected CNE-2Z cells by Bac-NIS and Bac-GFP were measured. Cell colony formation tests were conducted to evaluate the killing effect of Bac-NIS-mediated 131I. Based on the results, the transduction efficiency of Bac-GFP at the MOI of 200 or 400 reached 91.16 and 94.79%, respectively. NIS protein was expressed accurately on transfected CNE-2Z cell membranes and performed its normal function in iodine transport. Baculovirus had hardly any cytotoxic effects on infected cells, while relatively high concentration of sodium butyrate generated cytotoxicity. The correlation coefficient between the GFP fluorescence intensity and radioactivity in co-infected CNE-2Z cells was 0.917. Treatment coupled Bac-NIS with 131I killed the infected tumour cells dramatically in vitro. These results suggest that baculovirus is an effective vector of the gene delivery into CNE-2Z cells and NIS-mediated iodine transport is a potential approach for molecular imaging and radionuclide therapy of NPC.
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Structure-Property Relationships and (1) O2 Photosensitisation in Sterically Encumbered Diimine Pt(II) Acetylide Complexes.
Chemistry
PUBLISHED: 02-26-2013
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A series of sterically encumbered [Pt(L)(?-acetylide)2 ] complexes were prepared in which L, a dendritic polyaromatic diimine ligand, was held constant (L=1-(2,2-bipyrid-6-yl)-2,3,4,5-tetrakis(4-tert-butylphenyl)benzene) and the cis ethynyl co-ligands were varied. The optical properties of the complexes were tuned by changing the electronic character, extent of ? conjugation and steric bulk of the ethynyl ligands. Replacing electron-withdrawing phenyl-CF3 substituents (4) with electron-donating pyrenes (5) resulted in a red shift of both the lowest-energy absorption (?E=3300?cm(-1) , 61?nm) and emission bands (?E=1930?cm(-1) , 64?nm). The emission, assigned in each case as phosphorescence on the basis of the excited-state lifetimes, switched from being (3) MMLLCT-derived (mixed metal-ligand-to-ligand charge transfer) when phenyl/polyphenylene substituents (3, 4, 6) were present, to ligand-centred (3) ??* when the substituents were more conjugated aromatic platforms [pyrene (5) or hexa-peri-hexabenzocoronene (7)]. The novel Pt(II) acetylide complexes 5 and 7 absorb strongly in the visible region of the electromagnetic spectrum, which along with their long triplet excited-state lifetimes suggested they would be good candidates for use as singlet-oxygen photosensitisers. Determined by in situ photooxidation of 1,5-dihydroxynaphthalene (DHN), the photooxidation rate with pyrenyl-5 as sensitiser (kobs =39.3×10(-3) ?min(-1) ) was over half that of the known (1) O2 sensitiser tetraphenylporphyrin (kobs =78.6×10(-3) ?min(-1) ) under the same conditions. Measured (1) O2 quantum yields of complexes 5 and 7 were half and one-third, respectively, of that of TPP, and thus reveal an efficient triplet-triplet energy-transfer process in both cases.
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A new two-dimensional oligothiophene end-capped with alkyl cyanoacetate groups for highly efficient solution-processed organic solar cells.
Chem. Commun. (Camb.)
PUBLISHED: 02-22-2013
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A new two-dimensional small molecule (DCA3T(VT)BDT) with an acceptor-donor-acceptor framework showed a high power conversion efficiency of 4% with a high fill factor of up to 0.63 in solution-processed organic solar cells.
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Discovery and evaluation of piperid-4-one-containing mono-carbonyl analogs of curcumin as anti-inflammatory agents.
Bioorg. Med. Chem.
PUBLISHED: 02-13-2013
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We previously reported the design and discovery of three series of 5-carbon linker-containing mono-carbonyl analogs of curcumin (MCACs) as excellent anti-inflammatory agents. In continuation of our ongoing research, we designed and synthesized the fourth series of MCACs, whose central linker is a piperid-4-one. Their inhibitory effects against IL-6 production were evaluated in lipopolysaccharide (LPS)-stimulated macrophages. Among them, compounds F8, F29, F33, F35, and F36 exhibited the IC50 values under 5 ?M. The structure-activity relationship was discussed. Mechanistically, F35 and F36 dose-dependently prevented LPS-induced NF-?B and ERK activation. Finally, pretreatment with F35 and F36 significantly protected the C57B/L6 mice from LPS-induced septic death. Together, these data present a series of new analogs of curcumin as promising anti-inflammatory agents.
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Direct correlation of electrochemical behaviors with anti-thrombogenicity of semiconducting titanium oxide films.
J Biomater Appl
PUBLISHED: 02-13-2013
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Biomaterials-associated thrombosis is dependent critically upon electrochemical response of fibrinogen on material surface. The relationship between the response and anti-thrombogenicity of biomaterials is not well-established. Titanium oxide appears to have good anti-thrombogenicity and little is known about its underlying essential chemistry. We correlate their anti-thrombogenicity directly to electrochemical behaviors in fibrinogen containing buffer solution. High degree of inherent n-type doping was noted to contribute the impedance preventing charge transfer from fibrinogen into film (namely its activation) and consequently reduced degree of anti-thrombogenicity. The impedance was the result of high donor carrier density as well as negative flat band potential.
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Clinical application of iodine-eluting stent in patients with advanced esophageal cancer.
Oncol Lett
PUBLISHED: 01-19-2013
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The aim of the present study was to compare the clinical effectiveness of an iodine-eluting stent with a conventional stent in patients with advanced esophageal cancer. Patients with malignant esophageal cancer were randomly assigned to receive a conventional stent (group A) or an iodine-eluting stent (group B). Following implantation, the relief from dysphagia, survival time, routine blood tests, thyroid function examination and complications were compared in the two groups. Groups A and B consisted of 36 and 31 patients, respectively. The mean value that the dysphagia score decreased by was significantly lower in group A (0.83) compared with group B (1.65). The median survival time was longer in group B compared with group A (P=0.0022). No significant differences were observed in the severe complications between the two groups (P=0.084). The iodine-eluting esophageal stent is a relatively safe, feasible and effective treatment for malignant esophageal strictures.
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Efficient enhancement of the visible-light absorption of cyclometalated Ir(III) complexes triplet photosensitizers with Bodipy and applications in photooxidation and triplet-triplet annihilation upconversion.
Inorg Chem
PUBLISHED: 01-17-2013
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We report molecular designing strategies to enhance the effective visible-light absorption of cyclometalated Ir(III) complexes. Cationic cyclometalated Ir(III) complexes were prepared in which boron-dipyrromethene (Bodipy) units were attached to the 2,2-bipyridine (bpy) ligand via -C?C- bonds at either the meso-phenyl (Ir-2) or 2 position of the ? core of Bodipy (Ir-3). For the first time the effect of ? conjugating (Ir-3) or tethering (Ir-2) of a light-harvesting chromophore to the coordination center on the photophysical properties was compared in detail. Ir(ppy)2(bpy) (Ir-1; ppy = 2-phenylpyridine) was used as model complex, which gives the typical weak absorption in visible range (? < 4790 M(-1) cm(-1) in region > 400 nm). Ir-2 and Ir-3 showed much stronger absorption in the visible range (? = 71,400 M(-1) cm(-1) at 499 nm and 83,000 M(-1) cm(-1) at 527 nm, respectively). Room-temperature phosphorescence was only observed for Ir-1 (?(em) = 590 nm) and Ir-3 (?(em) = 742 nm). Ir-3 gives RT phosphorescence of the Bodipy unit. On the basis of the 77 K emission spectra, nanosecond transient absorption spectra, and spin density analysis, we proposed that Bodipy-localized long-lived triplet excited states were populated for Ir-2 (?T = 23.7 ?s) and Ir-3 (87.2 ?s). Ir-1 gives a much shorter triplet-state lifetime (0.35 ?s). Complexes were used as singlet oxygen ((1)O2) photosensitizers in photooxidation. The (1)O2 quantum yield of Ir-3 (?? = 0.97) is ca. 2-fold of Ir-2 (?? = 0.52). Complexes were also used as triplet photosensitizer for TTA upconversion; upconversion quantum yields of 1.2% and 2.8% were observed for Ir-2 and Ir-3, respectively. Our results proved that the strong absorption of visible light of Ir-2 failed to enhance production of a triplet excited state. These results are useful for designing transition metal complexes that show effective strong visible-light absorption and long-lived triplet excited states, which can be used as ideal triplet photosensitizers in photocatalysis and TTA upconversion.
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The complete mitochondrial genome of Martes flavigula.
Mitochondrial DNA
PUBLISHED: 01-11-2013
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The complete mitogenome sequence of Martes flavigula was determined using long PCR. The genome was 16,549 bp in length and contained 13 protein-coding genes, 2 ribosomal RNA genes, 22 transfer RNA genes and 1 control region. The overall base composition of the heavy strand is A (32.48%), C (26.89%), T (26.51%) and G (14.12%). The base compositions present clearly the A-C skew, which is most obvious in the control region and protein-coding genes. The extended termination-associated sequence domain, the central conserved domain and the conserved sequence block domain are defined in the mitochondrial genome control region of M. flavigula.
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Anthropogenic halo disturbances alter landscape and plant richness: a ripple effect.
PLoS ONE
PUBLISHED: 01-09-2013
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Although anthropogenic landscape fragmentation is often considered as the primary threat to biodiversity, other factors such as immediate human disturbances may also simultaneously threaten species persistence in various ways. In this paper, we introduce a conceptual framework applied to recreation landscapes (RLs), with an aim to provide insight into the composite influences of landscape alteration accompanying immediate human disturbances on plant richness dynamics. These impacts largely occur at patch-edges. They can not only alter patch-edge structure and environment, but also permeate into surrounding natural matrices/patches affecting species persistence-here we term these "Halo disturbance effects" (HDEs). We categorized species into groups based on seed or pollen dispersal mode (animal- vs. wind-dispersed) as they can be associated with species richness dynamics. We evaluated the richness of the two groups and total species in our experimental landscapes by considering the distance from patch-edge, the size of RLs and the intensity of human use over a six-year period. Our results show that animal-dispersed species decreased considerably, whereas wind-dispersed species increased while their richness presented diverse dynamics at different distances from patch-edges. Our findings clearly demonstrate that anthropogenic HDEs produce ripple effects on plant, providing an experimental interpretation for the diverse responses of species to anthropogenic disturbances. This study highlights the importance of incorporating these composite threats into conservation and management strategies.
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Food availability and animal space use both determine cache density of eurasian red squirrels.
PLoS ONE
PUBLISHED: 01-01-2013
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Scatter hoarders are not able to defend their caches. A longer hoarding distance combined with lower cache density can reduce cache losses but increase the costs of hoarding and retrieving. Scatter hoarders arrange their cache density to achieve an optimal balance between hoarding costs and main cache losses. We conducted systematic cache sampling investigations to estimate the effects of food availability on cache patterns of Eurasian red squirrels (Sciurus vulgaris). This study was conducted over a five-year period at two sample plots in a Korean pine (Pinus koraiensis)-dominated forest with contrasting seed production patterns. During these investigations, the locations of nest trees were treated as indicators of squirrel space use to explore how space use affected cache pattern. The squirrels selectively hoarded heavier pine seeds farther away from seed-bearing trees. The heaviest seeds were placed in caches around nest trees regardless of the nest tree location, and this placement was not in response to decreased food availability. The cache density declined with the hoarding distance. Cache density was lower at sites with lower seed production and during poor seed years. During seed mast years, the cache density around nest trees was higher and invariant. The pine seeds were dispersed over a larger distance when seed availability was lower. Our results suggest that 1) animal space use is an important factor that affects food hoarding distance and associated cache densities, 2) animals employ different hoarding strategies based on food availability, and 3) seed dispersal outside the original stand is stimulated in poor seed years.
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Identifying the genome-wide sequence variations and developing new molecular markers for genetics research by re-sequencing a Landrace cultivar of foxtail millet.
PLoS ONE
PUBLISHED: 01-01-2013
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Foxtail millet (Setariaitalica) is a drought-resistant, barren-tolerant grain crop and forage. Currently, it has become a new model plant for cereal crops and biofuel grasses. Although two reference genome sequences were released recently, comparative genomics research on foxtail millet is still in its infancy. Using the Solexa sequencing technology, we performed genome re-sequencing on one important foxtail millet Landrace, Shi-Li-Xiang (SLX). Compared with the two reference genome sequences, the following genetic variation patterns were identified: 762,082 SNPs, 26,802 insertion/deletion polymorphisms of 1 to 5 bp in length (indels), and 10,109 structural variations (SVs) between SLX and Yugu1 genomes; 915,434 SNPs, 28,546 indels and 12,968 SVs between SLX and Zhang gu genomes. Furthermore, based on the Yugu1 genome annotation, we found out that ~ 40% SNPs resided in genes containing NB-ARC domain, protein kinase or leucine-rich repeats, which had higher non-synonymous to synonymous SNPs ratios than average, suggesting that the diversification of plant disease resistance proteins might be caused by pathogen pressure. In addition, out of the polymorphisms identified between SLX and Yugu1, 465 SNPs and 146 SVs were validated with more than 90% accuracy, which could be used as DNA markers for whole-genome genotyping and marker-assisted breeding. Here, we also represented an example of fine mapping and identifying a waxy locus in SLX using these newly developed DNA markers. This work provided important information that will allow a deeper understanding of the foxtail millet genome and will be helpful for dissecting the genetic basis of important traits in foxtail millet.
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Excited state intramolecular proton transfer (ESIPT): from principal photophysics to the development of new chromophores and applications in fluorescent molecular probes and luminescent materials.
Phys Chem Chem Phys
PUBLISHED: 12-21-2011
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In this perspective we introduce the basic photophysics of the excited-state intramolecular proton transfer (ESIPT) chromophores, then the state-of-the-art development of the ESIPT chromophores and their applications in chemosensors, biological imaging and white-light emitting materials are summarized. Most of the applications of the ESIPT chromophores are based on the photophysics properties, such as design of fluorescent chemosensors by perturbation of the ESIPT process upon interaction with the analytes, their use as biological fluorescent tags to study DNA-protein interaction by probing the variation of the hydration, or design of white-light emitting materials by employing the large Stokes shift of the ESIPT chromophores (to inhibit the Föster energy transfer of the components). The photophysical mechanism of these applications is discussed. Furthermore, a new research topic concerning the ESIPT chromophores is proposed based on our groups results, that is, to develop organic triplet sensitizers with ESIPT chromophores.
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(E)-3-(2,4-Dimeth-oxy-phen-yl)-1-(3,4,5-trimeth-oxy-phen-yl)prop-2-en-1-one.
Acta Crystallogr Sect E Struct Rep Online
PUBLISHED: 12-04-2011
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In the title chalcone derivative, C(20)H(22)O(6), the dihedral angle between the mean planes of the benzene rings is 15.77?(6)°. The H atoms of the central C=C double bond are in a trans configuration. There are a number of C-H?O interactions and a C-H?? interaction present in the crystal structure.
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Evaluation and discovery of novel synthetic chalcone derivatives as anti-inflammatory agents.
J. Med. Chem.
PUBLISHED: 11-04-2011
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Major anti-inflammatory agents, steroids and cyclooxygenase, were proved to have serious side effects. Here, a series of chalcone derivatives were synthesized and screened for anti-inflammatory activities. QSAR study revealed that the presence of electron-withdrawing groups in B-ring and electron-donating groups in A-ring of chalcones was important for inhibition of LPS-induced IL-6 expression. Further, compounds 22, 23, 26, 40, and 47 inhibited TNF-? and IL-6 release in a dose-dependent manner and decreased LPS-induced TNF-?, IL-1?, IL-6, IL-12, and COX-2 mRNA production. Mechanistically, compounds 23 and 26 interfered with JNK/NF-?B signaling and dose-dependently prevented ERK and p38 activation. In addition, 23 and 26 exhibited a significant protection against LPS-induced death and were able to block high glucose-activated cytokine profiles in macrophages. Together, these data show a series of anti-inflammatory chalcones with potential therapeutic effects in inflammatory diseases.
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Colorimetric and ratiometric fluorescent chemosensor based on diketopyrrolopyrrole for selective detection of thiols: an experimental and theoretical study.
J. Org. Chem.
PUBLISHED: 10-27-2011
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A colorimetric and ratiometric fluorescent thiol probe was devised with diketopyrrolopyrrole (DPP) fluorophore. The probe gives absorption and emission at 523 and 666 nm, respectively. In the presence of thiols, such as cysteine, the absorption and emission band shifted to 479 and 540 nm, respectively. Correspondingly, the color of the probe solution changed from purple to yellow, and the fluorescence changed from red to yellow. The emission intensity at 540 nm was enhanced by 140-fold. The Stokes shift of probe 1 (107 nm) is much larger than the unsubstituted DPP fluorophore (56 nm). Mass spectral analysis demonstrated that besides the expected Michael addition of thiols to the C?C bonds, the CN groups of the malonitrile moieties also react with thiols to form 4,5-dihydrothiazole structure. Probe 1 was used for fluorescence imaging of intracellular thiols. In the presence of thiols, both the green and red channel of the microscopy are active. With removal of the intracellular thiols, signal can only be detected through the red channel; thus, ratiometric bioimaging of intracellular thiols was achieved. The ratiometric response of probe 1 was rationalized by DFT calculations. Our complementary experimental and theoretical studies will be useful for design of ratiometric/colorimetric molecular probes.
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Long-lived room temperature deep-red/near-IR emissive intraligand triplet excited state (3IL) of naphthalimide in cyclometalated platinum(II) complexes and its application in upconversion.
Inorg Chem
PUBLISHED: 10-26-2011
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[C(^)NPt(acac)] (C(^)N = cyclometalating ligand; acac = acetylacetonato) complexes in which the naphthalimide (NI) moiety is directly cyclometalated (NI as the C donor of the C-Pt bond) were synthesized. With 4-pyrazolylnaphthalimide, isomers with five-membered (Pt-2) and six-membered (Pt-3) chelate rings were obtained. With 4-pyridinylnaphthalimide, only the complex with a five-membered chelate ring (Pt-4) was isolated. A model complex with 1-phenylpyrazole as the C(^)N ligand was prepared (Pt-1). Strong absorption of visible light (? = 21,900 M(-1) cm(-1) at 443 nm for Pt-3) and room temperature (RT) phosphorescence at 630 nm (Pt-2 and Pt-3) or 674 nm (Pt-4) were observed. Long-lived phosphorescences were observed for Pt-2 (?(P) = 12.8 ?s) and Pt-3 (?(P) = 61.9 ?s). Pt-1 is nonphosphorescent at RT in solution because of the acac-localized T(1) excited state [based on density functional theory (DFT) calculations and spin density analysis], but a structured emission band centered at 415 nm was observed at 77 K. Time-resolved transient absorption spectra and spin density analysis indicated a NI-localized intraligand triplet excited state ((3)IL) for complexes Pt-2, Pt-3, and Pt-4. DFT calculations on the transient absorption spectra (T(1) ? T(n) transitions, n > 1) also support the (3)IL assignment of the T(1) excited states of Pt-2, Pt-3, and Pt-4. The complexes were used as triplet sensitizers for triplet-triplet-annihilation (TTA) based upconversion, and the results show that Pt-3 is an efficient sensitizer with an upconversion quantum yield of up to 14.1%, despite its low phosphorescence quantum yield of 5.2%. Thus, we propose that the sensitizer molecules at the triplet excited state that are otherwise nonphosphorescent were involved in the TTA upconversion process, indicating that weakly phosphorescent or nonphosphorescent transition-metal complexes can be used as triplet sensitizers for TTA upconversion.
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Tuning the emissive triplet excited states of platinum(II) Schiff base complexes with pyrene, and application for luminescent oxygen sensing and triplet-triplet-annihilation based upconversions.
Dalton Trans
PUBLISHED: 10-20-2011
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Pt(II) Schiff base complexes containing pyrene subunits were prepared using the chemistry-on-complex approach. This is the first time that supramolecular photochemical approach has been used to tune the photophysical properties of Schiff base Pt(II) complexes, such as emission wavelength and lifetimes. The complexes show intense absorption in the visible region (? = 13100 M(-1) cm(-1) at 534 nm) and red phosphorescence at room temperature. Notably, much longer triplet excited state lifetimes (? = 21.0 ?s) were observed, compared to the model complexes (? = 4.4 ?s). The extension of triplet excited state lifetimes is attributed to the establishment of equilibrium between the metal-to-ligand charge-transfer ((3)MLCT) state (coordination centre localized) and the intraligand ((3)IL) state (pyrene localized), or population of the long-lived (3)IL triplet excited state. These assignments were fully rationalized by nanosecond time-resolved difference absorption spectra, 77 K emission spectra and density functional theory calculations. The complexes were used as triplet sensitizers for triplet-triplet-energy-tranfer (TTET) processes, i.e. luminescent O(2) sensing and triplet-triplet annihilation (TTA) based upconversion. The O(2) sensitivity (Stern-Volmer quenching constant) of the complexes was quantitatively evaluated in polymer films. The results show that the O(2) sensing sensitivity of the pyrene containing complex (K(SV) = 0.04623 Torr(-1)) is 15-fold of the model complex (K(SV) = 0.00313 Torr(-1)). Furthermore, significant TTA upconversion (upconversion quantum yield ?(UC) = 17.7% and the anti-Stokes shift is 0.77 eV) was observed with pyrene containing complexes being used as triplet sensitizers. Our approach to tune the triplet excited states of Pt(II) Schiff base complexes will be useful for the design of phosphorescent transition metal complexes and their applications in light-harvesting, photovoltaics, luminescent O(2) sensing and upconversion, etc.
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Ratiometric luminescent molecular oxygen sensors based on uni-luminophores of C^N Pt(II)(acac) complexes that show intense visible-light absorption and balanced fluorescence/phosphorescence dual emission.
Chem. Commun. (Camb.)
PUBLISHED: 09-26-2011
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Uni-luminophores of C^N cyclometalated Pt(II) complexes with balanced room temperature fluorescence/phosphorescence dual emission were prepared for ratiometric oxygen sensing in both intensity mode and lifetime mode.
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Organic triplet sensitizer library derived from a single chromophore (BODIPY) with long-lived triplet excited state for triplet-triplet annihilation based upconversion.
J. Org. Chem.
PUBLISHED: 08-09-2011
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Triplet-triplet annihilation (TTA) based upconversions are attractive as a result of their readily tunable excitation/emission wavelength, low excitation power density, and high upconversion quantum yield. For TTA upconversion, triplet sensitizers and acceptors are combined to harvest the irradiation energy and to acquire emission at higher energy through triplet-triplet energy transfer (TTET) and TTA processes. Currently the triplet sensitizers are limited to the phosphorescent transition metal complexes, for which the tuning of UV-vis absorption and T(1) excited state energy level is difficult. Herein for the first time we proposed a library of organic triplet sensitizers based on a single chromophore of boron-dipyrromethene (BODIPY). The organic sensitizers show intense UV-vis absorptions at 510-629 nm (? up to 180,000 M(-1) cm(-1)). Long-lived triplet excited state (?(T) up to 66.3 ?s) is populated upon excitation of the sensitizers, proved by nanosecond time-resolved transient difference absorption spectra and DFT calculations. With perylene or 1-chloro-9,10-bis(phenylethynyl)anthracene (1CBPEA) as the triplet acceptors, significant upconversion (?(UC) up to 6.1%) was observed for solution samples and polymer films, and the anti-Stokes shift was up to 0.56 eV. Our results pave the way for the design of organic triplet sensitizers and their applications in photovoltaics and upconversions, etc.
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pH-dependent conformational change of Fe(3+)-binding giant DNA for control of aggregation of gold nanoparticles.
J Nanosci Nanotechnol
PUBLISHED: 07-21-2011
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The pH-dependent conformational change of Calf thymus DNA (ctDNA, a typical giant DNA) binding with Fe3+ (Fe(3+)-ctDNA) for control of aggregation of gold nanoparticles (AuNPs) hybridized with Fe(3+)-ctDNA was described, which was attributed to the interaction between ctDNA and Fe3+. In acidic conditions, significant conformational change of ctDNA from elongated coil state to folded compact state occurs by binding of Fe3+ with the phosphate groups of ctDNA. The SPR absorbance and thus the colors of AuNPs hybridized with Fe(3+)-ctDNA would vary pH-dependently within the pH range 6.0-10.6 as the folded compact ctDNA could not stabilize AuNPs as effectively as the elongated coil ctDNA. Zeta potentials and Raman spectra were studied for revealing the interaction between Fe3+ and ctDNA as well as that between AuNPs and DNA (ctDNA and Fe(3+)-ctDNA). The conformational change of ctDNA driven by Fe3+ was also investigated using CD spectroscopy. This study prompts the possibility that the spectral, and thus color, change of AuNPs can be used to follow the conformational change of giant DNA driven by metal ions and biological relevant pH conditions.
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Enantioselective recognition of mandelic acid by a 3,6-dithiophen-2-yl-9H-carbazole-based chiral fluorescent bisboronic acid sensor.
J. Org. Chem.
PUBLISHED: 06-16-2011
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We have prepared chiral fluorescent bisboronic acid sensors with 3,6-dithiophen-2-yl-9H-carbazole as the fluorophore. The thiophene moiety was used to extend the ?-conjugation framework of the fluorophore in order to red-shift the fluorescence emission and, at the same time, to enhance the novel process where the fluorophore serves as the electron donor of the photoinduced electron transfer process (d-PET) of the boronic acid sensors; i.e., the background fluorescence of the sensor 1 at acidic pH is weaker compared to that at neutral or basic pH, in stark contrast to the typical a-PET boronic acid sensors (where the fluorophore serves as the electron acceptor of the photoinduced electron transfer process). The benefit of the d-PET boronic acid sensors is that the recognition of the hydroxylic acids can be achieved at acidic pH. We found that the thiophene moiety is an efficient ?-conjugation linker and electron donor; as a result, the d-PET contrast ratio of the sensors upon variation of the pH is improved 10-fold when compared to the previously reported d-PET sensors without the thiophene moiety. Enantioselective recognition of tartaric acid was achieved at acid pH, and the enantioselectivity (total response K(D)I(F)(D)/K(L)I(F)(L)) is 3.3. The fluorescence enhancement (I(F)(Sample)/I(F)(Blank)) of sensor 1 upon binding with tartaric acid is 3.5-fold at pH 3.0. With the fluorescent bisboronic acid sensor 1, enantioselective recognition of mandelic acid was achieved for the first time. To the best of our knowledge, this is the first time that the mandelic acid has been enantioselectively recognized using a chiral fluorescent boronic acid sensor. Chiral monoboronic acid sensor 2 and bisboronic acid sensor 3 without the thiophene moiety failed to enantioselectively recognize mandelic acid. Our findings with the thiophene-incorporated boronic acid sensors will be important for the design of d-PET fluorescent sensors for the enantioselective recognition of ?-hydroxylic acids such as mandelic acid, given that it is currently a challenge to recognize these analytes with boronic acid fluorescent molecular sensors.
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Coumarin phosphorescence observed with N^N Pt(II) bisacetylide complex and its applications for luminescent oxygen sensing and triplet-triplet-annihilation based upconversion.
Dalton Trans
PUBLISHED: 06-08-2011
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A dbbpy platinum(II) bis(coumarin acetylide) complex (Pt-1, dbbpy = 4,4-di-tert-butyl-2,2-bipyridine) was prepared. Pt-1 shows intense absorption in the visible region (?(abs) = 412 nm, ? = 3.23 × 10(4) M(-1) cm(-1)) compared to the model complex dbbpy Pt(II) bis(phenylacetylide) (Pt-2, ?(abs) = 424 nm, ? = 8.8 × 10(3) M(-1) cm(-1)). Room temperature phosphorescence was observed for Pt-1 ((3)IL, ?(P) = 2.52 ?s, ?(em) = 624 nm, ?(P) = 2.6%) and the emissive triplet excited state was assigned as mainly intraligand triplet excited state ((3)IL), proved by 77 K steady state emission, nanosecond time-resolved transient absorption spectroscopy and DFT calculations. Complex Pt-1 was used for phosphorescent oxygen sensing and the sensitivity (Stern-Volmer quenching constant K(SV) = 0.012 Torr(-1)) is 12-fold of the model complex Pt-2 (K(SV) = 0.001 Torr(-1)). Pt-1 was also used as triplet sensitizer for triplet-triplet-annihilation based upconversion, upconversion quantum yield ?(UC) up to 14.1% was observed, vs. 8.9% for the model complex Pt-2.
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Accessing the long-lived near-IR-emissive triplet excited state in naphthalenediimide with light-harvesting diimine platinum(II) bisacetylide complex and its application for upconversion.
Dalton Trans
PUBLISHED: 05-19-2011
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Room temperature near-IR phosphorescence of naphthalenediimide (NDI) was observed with N^N Pt(II) bisacetylide complex (Pt-NDI) in which the NDI was connected to Pt(II) center via acetylide. Pt-NDI shows intense absorption of visible light and long-lived NDI-localized excited state ((3)IL) (?(T) = 22.3 ?s). Pt-NDI was used as a triplet sensitizer for upconversion.
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Highly efficient CdS quantum dot-sensitized solar cells based on a modified polysulfide electrolyte.
J. Am. Chem. Soc.
PUBLISHED: 05-12-2011
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A modified polysulfide redox couple, [(CH(3))(4)N](2)S/[(CH(3))(4)N](2)S(n), in an organic solvent (3-methoxypropionitrile) was employed in CdS quantum dot (QD)-sensitized solar cells (QDSSCs), and an unprecedented energy conversion efficiency of up to 3.2% was obtained under AM 1.5 G illumination. The QDs were linked to nanoporous TiO(2) via covalent bonds by using thioglycolic acid, and chemical bath deposition in an organic solvent was then used to prepare the QDSSCs, facilitating high wettability and superior penetration capability of the TiO(2) films. A very high fill factor of 0.89 was observed with the optimized QDSSCs.
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Accessing the long-lived emissive 3IL triplet excited states of coumarin fluorophores by direct cyclometallation and its application for oxygen sensing and upconversion.
Dalton Trans
PUBLISHED: 05-04-2011
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We studied four cyclometallated Pt(II) complexes, in which the thiazo-coumarin ligands (Pt-2, Pt-3 and Pt-4) or the phenylthiazo ligand (Pt-1) were directly cycloplatinated. Pt-2 shows intense absorption in visible region but other complexes show blue-shifted absorption. Room temperature phosphorescence was observed for all the complexes, and the emission wavelength is dependent on the size of the ?-conjugation, not the intramolecular charge transfer (ICT) feature of the C^N ligands. Pt-2 shows longer phosphorescence lifetime (? = 20.3 ?s) than other complexes (below 2.0 ?s). Furthermore, Pt-2 shows phosphorescence quantum yield ? = 0.37, whereas Pt-3 and Pt-4 show much smaller ? values (0.03 and 0.01, respectively). DFT/TDDFT calculations indicate (3)IL triplet excited states for the complexes. The complexes were used as for luminescence O(2) sensing and triplet-triplet-annihilation (TTA) based upconversion. Stern-Volmer quenching constant K(SV) = 0.026 Torr(-1) was observed for Pt-2, ca. 89-fold of that of Pt-3. TTA upconversion is achieved with Pt-2 (?(em) = 400 nm with ?(ex) = 473 nm, anti-Stokes shift is 0.47 eV, excitation power density is at 70 mW cm(-2)). The upconversion quantum yield with Pt-2 as triplet sensitizer is up to 15.4%. The TTET efficiency (K(SV) = 1.33 × 10(5) M(-1), k(q) = 6.57 × 10(9) M(-1) s(-1). DPA as quencher) of Pt-2 is 34-fold of the model complex [Ru(dmb)(3)][PF(6)](2). Our results show that the (3)IL state can be readily accessed by direct cyclometallation of organic fluorophores and this approach will be useful for preparation and applications of transition metal complexes that show intense absorption in visible region and the long-lived emissive (3)IL excited states.
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(E)-1-(4-Meth-oxy-phen-yl)-3-(2,4,6-trimeth-oxy-phen-yl)prop-2-en-1-one.
Acta Crystallogr Sect E Struct Rep Online
PUBLISHED: 04-23-2011
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In the title compound, C(19)H(20)O(5), the dihedral angle between the two aromatic rings is 18.23?(4)°. The crystal structure exhibits only weak C-H?? and C-H?O contacts between the mol-ecules.
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Highly selective fluorescent OFF-ON thiol probes based on dyads of BODIPY and potent intramolecular electron sink 2,4-dinitrobenzenesulfonyl subunits.
Org. Biomol. Chem.
PUBLISHED: 04-12-2011
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Two highly selective OFF-ON green emitting fluorescent thiol probes (1 and 2) with intense absorption in the visible spectrum (molar extinction coefficient ? is up to 73?800 M(-1) cm(-1) at 509 nm) based on dyads of BODIPY (as electron donor of the photo-induced electron transfer, i.e.PET) and 2,4-dinitrobenzenesulfonyl (DNBS) (as electron acceptor of the PET process) were devised. The single crystal structures of the two probes were determined. The distance between the electron donor (BODIPY fluorophore) and the electron acceptor (DNBS) of probe 2 is larger than that of probe 1, as a result the contrast ratio (or the PET efficiency) of probe 2 is smaller than that of probe 1. However, fluorescence OFF-ON switching effects were observed for both probe 1 and probe 2 in the presence of cysteine (the emission enhancement is 300-fold for probe 1 and 54-fold for probe 2). The fluorescence OFF-ON sensing mechanism is rationalized by DFT/TDDFT calculations. We demonstrated with DFT calculations that DNBS is ca. 0.76 eV more potent to accept electrons than the maleimide moiety. The probes were used for fluorescent imaging of cellular thiols.
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Enantioselective recognition of tartaric acids with ethynylated carbazole-based chiral bisboronic acid chemosensors with improved response at acidic pH.
J Fluoresc
PUBLISHED: 03-22-2011
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Chiral bisboronic acid chemosensors based on ethynylated carbazole were prepared. The chiral chemosensors show red-shifted emission than the chemosensors with unsubstituted carbazole fluorophore. a-PET effect was found for the chemosensors, which is different from our previous observation of the d-PET effect for boronic acid chemosensors based on carbazole. Enantioselective recognition of tartaric acids was implicated with these chemosensors. Consecutive fluorescence emission enhancement/diminishment were observed with increasing the concentration of the tartaric acids, which is tentatively assigned to the transition of the binding stoichiometry from 1:1 binding to 1:2 binding. In particularly interesting is the improved fluorescence response at acidic pH for recognition of tartaric acids, which is rarely observed for a-PET chemosensors. We propose that the sensing is due to hybrid mechanism of a-PET/d-PET and conformational restriction upon binding. Our results will be useful for design of chiral boronic acid chemosensors with improved fluorescence response at acidic pH, which are rarely reported.
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