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Recently, the application of computational tools to the rational design of catalysts has received considerable attention, but progress has been limited by the reliance on databases and because mechanistic data have been almost neglected. Herein, we report a new strategy for catalyst design, designated catalyst-oriented design based on elementary reactions (CODER), which fully utilizes mechanistic data, combines the strengths of computational tools and researcher experience. CODER enabled the development of extremely efficient Pd catalysts for C-N coupling, which markedly improved the efficiency of the synthesis of widely used triarylamine optoelectronic materials by enhancing the turnover numbers (up to 340000) to 1-3 orders of magnitude towards literature values.
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New practical synthesis of 2-amino-1,3-selenazole with transition metal-free multicomponent reaction is reported here. A series of 2-amino-1,3-selenazole derivatives were afforded by the nucleophilic addition of amines to isoselenocyanate formed in situ, followed by Michael addition reaction and aromatization. The products were isolated from moderate to excellent yields.
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Efficient Cs+-Sr2+ separation, highly desirable for radionuclide recovery in medical and industrial applications, was achieved by the ion exchange technique over a novel microporous silver selenidostannate, [NH3CH3]0.5[NH2(CH3)2]0.25Ag1.25SnSe3 (AgSnSe-1). This material was synthesized in deep eutectic solvent (DES), where the alkylammonium cations play significant structure-directing roles in the construction of micropores that allow for selective ion exchange toward Cs+ against Sr2+. The much greater KdCs (1.06 × 104 mL g-1) over KdSr (87.7 mL g-1) contributes to an outstanding separation factor SFCs/Sr of â¼121.4 that is top-ranked among inorganic materials. An ion exchange column filled with AgSnSe-1 exhibits a remarkable separation effect for 10â¯000 bed volumes of continuous flow, with removal rates of â¼99.9% and â¼0 ± 5.5% for Cs+ and Sr2+, respectively. AgSnSe-1 exhibits excellent ß and γ radiation resistances and a chemical stability over a broad pH range of 1-12. The Se leaching level below the safe guideline value for drinking water highlights the environmental-friendly nature of AgSnSe-1. The high Cs+ exchange performance is almost unaffected by Na+, Mg2+, and Ca2+ cations. The Cs+-laden product AgSnSe-1Cs can be facilely eluted for recycling use, highlighting the great potential of open framework metal selenides in nuclear waste treatment and renewable energy utilization.
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In this article, we report the design, synthesis, and characterization of a series of cyclometalated iridium(III) polypyridine complexes containing a perfluorobiphenyl (PFBP) moiety [Ir(N^C)2(bpy-PFBP)](PF6) (bpy-PFBP = 4-(S-(perfluoro-(1,1'-biphenyl)-4-yl)-N-mercaptoethylaminocarbonyloxymethyl)-4'-methyl-2,2'-bipyridine; HN^C = 2-phenylpyridine (Hppy) (1a), 2-(4-hydroxymethylphenyl)pyridine (Hppy-CH2OH) (2a), 2-((1,1'-biphenyl)-4-yl)pyridine (Hpppy) (3a), 2-((4'-hydroxymethyl-1,1'-biphenyl)-4-yl)pyridine (Hpppy-CH2OH) (4a), 2-phenylquinoline (Hpq) (5a), 2-(4-hydroxymethylphenyl)quinoline (Hpq-CH2OH) (6a)). Their PFBP-free counterparts [Ir(N^C)2(bpy-C4)](PF6) (bpy-C4 = 4-(N-n-butylaminocarbonyloxymethyl)-4'-methyl-2,2'-bipyridine; HN^C = Hppy (1b), Hppy-CH2OH (2b), Hpppy (3b), Hpppy-CH2OH (4b), Hpq (5b), Hpq-CH2OH (6b)) were also prepared for comparison studies. Upon irradiation, all the complexes displayed intense and long-lived greenish-yellow to orange luminescence in solutions under ambient conditions and in low-temperature alcohol glass. Reactions of the PFBP complexes with peptides containing the FCPF sequence via the π-clamp-mediated cysteine conjugation afforded luminescent peptide conjugates that exhibited rich photophysical properties. Using complex 3a as an example, we demonstrated that the conjugation of complexes to organelle-targeting peptides is an effective means to modulate their intracellular localization behavior, which was further shown to be important to their performance in photodynamic therapy. The results of this work will contribute to the development of photofunctional transition metal complexes as theranostic agents.
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Compuestos de Bifenilo/farmacología , Complejos de Coordinación/farmacología , Sustancias Luminiscentes/farmacología , Piridinas/farmacología , Fármacos Sensibilizantes a Radiaciones/farmacología , Compuestos de Bifenilo/metabolismo , Compuestos de Bifenilo/efectos de la radiación , Núcleo Celular/metabolismo , Complejos de Coordinación/metabolismo , Complejos de Coordinación/efectos de la radiación , Retículo Endoplásmico/metabolismo , Células HeLa , Humanos , Iridio/química , Iridio/efectos de la radiación , Luz , Sustancias Luminiscentes/metabolismo , Sustancias Luminiscentes/efectos de la radiación , Microscopía Confocal , Péptidos/metabolismo , Péptidos/farmacología , Medicina de Precisión , Piridinas/metabolismo , Piridinas/efectos de la radiación , Fármacos Sensibilizantes a Radiaciones/metabolismo , Fármacos Sensibilizantes a Radiaciones/efectos de la radiación , Oxígeno Singlete/metabolismoRESUMEN
BACKGROUND The study aimed to explore the genetic association of Fc receptor-like 5 (FCRL5) gene variants (rs6427384 and rs6692977) with ankylosing spondylitis risk in Chinese Han population. MATERIAL AND METHODS Genotyping for FCRL5 gene variations rs6427384 and rs6692977 was implemented among 130 ankylosing spondylitis cases and 135 healthy persons, through polymerase chain reaction restriction fragment length polymorphism (PCR-RFLP) method. Frequency dissimilarity for 2 polymorphisms was compared between 2 groups using chi-square test. The association strength of FCRL5 gene polymorphism with ankylosing spondylitis risk was estimated by odds ratios with 95% confidence intervals. RESULTS The frequencies of rs6427384 CC genotype and C allele were significantly lower in the case group than that in the control group (P<0.05), which suggested that C allele of rs6427384 polymorphism might offer protection against ankylosing spondylitis onset. Whereas only 2 genotypes of rs6692977 were detected in the control group, and no significant association was found with ankylosing spondylitis susceptibility. CONCLUSIONS FCRL5 gene polymorphism rs6427384 was correlated to ankylosing spondylitis occurrence among Chinese Han population, while rs6692977 was not.
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Predisposición Genética a la Enfermedad/genética , Receptores Fc/genética , Espondilitis Anquilosante/genética , Adulto , Pueblo Asiatico/genética , Estudios de Casos y Controles , China , Femenino , Humanos , Masculino , Polimorfismo de Nucleótido Simple , Factores de RiesgoRESUMEN
This communication reports novel luminescent rhenium(I)-polypyridine complexes appended with a perylene diimide (PDI) or benzoperylene monoimide (BPMI) moiety through a non-conjugated linker. The photophysical and photochemical properties originating from the interactions of the metal polypyridine and perylene units were exploited to afford new cellular reagents with thiol-sensing capability and excellent photocytotoxic activity.
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Complejos de Coordinación/química , Sustancias Luminiscentes/química , Perileno/análogos & derivados , Piridinas/química , Renio/química , Supervivencia Celular/efectos de los fármacos , Complejos de Coordinación/toxicidad , Transferencia Resonante de Energía de Fluorescencia , Células HeLa , Humanos , Sustancias Luminiscentes/toxicidad , Microscopía Confocal , Imagen Óptica , Piridinas/toxicidad , Renio/toxicidad , Compuestos de Sulfhidrilo/análisisRESUMEN
Deep eutectic solvents (DESs) have been adopted as reaction media for solvothermal synthesis of crystal materials. In the present work, we extended the scope of DESs in chalcogenidometalate preparation by including dimethylamine, ethylamine, and trimethylamine hydrochlorides and synthesized a series of novel Sn-Se and Ag-Sn-Se compounds: i.e., [NH2(CH3)2]2Sn3Se7·0.5NH(CH3)2 (1), [NH4]2Sn4Se9 (2), [NH3C2H5]2Sn3Se7 (3), and [NH4]3AgSn3Se8 (4). Compounds 1 and 3 possess honeycomb lamellar [Sn3Se7] n2 n- structures featuring large hexagonal windows, while compound 2 features a rare [Sn4Se9] n2 n- anionic layer consisting of tetrameric {Sn4Se10} clusters as secondary building units (SBUs). Compound 4 comprises infinite [AgSn3Se8] n3 n- chains built by {Sn3Se8} units with Ag+ linkers, and it represents the first heterometallic chalcogenide synthesized in DESs. The organic ammonium cations of halide salts or in situ formed ammonium cations from the decomposition of urea act as templating agents for the formation of the inorganic frameworks. Compound 4 exhibits a marked thermochromic performance in the visible light range owing to the negative temperature dependence of its band gap ( Eg = 2.305-2.119 eV in the range of 100-450 K). The gold-dark red-gold color change is highly reversible in five rounds of heating and cooling, without any phase transition of the material, shedding light on the consequent device innovations.
RESUMEN
Rational synthesis of inorganic matter remains a great challenge encountered with modern synthetic chemistry. Here we reported the stepwise solvothermal conversion from GeO2 to [MGe4S10]n3n- (M = Cu, Ag) polymer via isolatable [Ge2S6]4- and [Ge4S10]4- anions by virtue of templating technique. The facile sulfuration of GeO2 resulted in the methylammonium-templated dimeric thiogermanate [CH3NH3]4Ge2S6 (1). This was used subsequently as a precursor for the formation of adamantane-like [Ge4S10]4- cluster, which was isolated as a mixed methylammonium/ethylammonium salt [CH3CH2NH3]3[CH3NH3]Ge4S10 (2). Compound 2 was then successfully used as a precursor to react with Cu+ and Ag+ cations in the presence of tetraethylammonium, resulting in alternating copolymeric products [(CH3CH2)4N]3MGe4S10 (M = Cu (3), Ag (4)), whose anionic moieties feature a novel zigzag chainlike structure constructed by [Ge4S10]4- clusters via two-coordinate Cu+/Ag+ linkers. Mixed amine/ethanol or deep eutectic solvents were applied as media for the syntheses of 1-4, and all the products were characterized in the solid state and solution. Crystal structural analysis of the title compounds revealed significant templating roles of the alkylammonium cations as both space-filling agents and hydrogen-bonding donors, suggesting the structure-directing mechanism for the species formation and crystal growth. The design and optimization of multistep structural conversion upon templating effects would be beneficial for drawing rational, predictable pathways for inorganic synthesis.
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Although the strain-promoted sydnone-alkyne cycloaddition reaction has been utilized for bioconjugation, its potential applications in bioorthogonal labeling and imaging in live cells have not been explored. This communication reports novel bioorthogonal imaging reagents with environment-sensitive emission properties through the modification of sydnone with cyclometalated iridium(III) polypyridine complexes. These complexes displayed significant emission enhancement and lifetime elongation upon reaction with strained alkyne derivatives, and were utilized to label cyclooctyne-modified proteins and ceramide molecules in live cells. Additionally, the manipulation of the photocytotoxicity of the complexes through the use of a bioorthogonal reagent was demonstrated.
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We report a new class of ruthenium(II) polypyridine complexes functionalized with a nitrone group as phosphorogenic bioorthogonal probes. These complexes were very weakly emissive owing to rapid C=N isomerization of the nitrone moiety, but exhibited significant emission enhancement upon strain-promoted alkyne-nitrone cycloaddition (SPANC) reaction with bicyclo[6.1.0]nonyne (BCN)-modified substrates. The modification of nitrone with a dicationic ruthenium(II) polypyridine unit at the α-C-position and a phenyl ring at the N-position led to remarkably accelerated reaction kinetics, which are substantially greater (up to ≈278 fold) than those of other acyclic nitrone-BCN systems. Interestingly, the complexes achieved specific cell membrane/cytosol staining upon specific labeling of an exogenous substrate, BCN-modified decane (BCN-C10), in live cells. Importantly, the in situ generation of the more lipophilic isoxazoline adduct in the cytoplasm resulted in increased cytotoxicity, highlighting a novel approach to apply the SPANC labeling technique in drug activation.
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Alquinos/química , Hidrocarburos Clorados/química , Indicadores y Reactivos/química , Óxidos de Nitrógeno/química , Rutenio/química , Reacción de Cicloadición , Humanos , Coloración y EtiquetadoRESUMEN
The silkworm (Bombyx mori) is an economically-important insect that can secrete silk. Carboxypeptidases have been found in various metazoan species and play important roles in physiological and biochemical reactions. Here, we analyzed the silkworm genome database and characterized 48 carboxypeptidases, including 34 metal carboxypeptidases (BmMCP1-BmMCP34) and 14 serine carboxypeptidases (BmSCP1-BmSCP14), to better understand their diverse functions. Compared to other insects, our results indicated that carboxypeptidases from silkworm have more family members. These silkworm carboxypeptidases could be divided into four families: Peptidase_M2 carboxypeptidases, Peptidase_M14 carboxypeptidases, Peptidase_S10 carboxypeptidases and Peptidase_S28 carboxypeptidases. Microarray analysis showed that the carboxypeptidases had distinct expression patterns, whereas quantitative real-time PCR demonstrated that the expression level of 13 carboxypeptidases significantly decreased after starvation and restored after re-feeding. Overall, our study provides new insights into the functional and evolutionary features of silkworm carboxypeptidases.
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Bombyx/genética , Carboxipeptidasas/clasificación , Carboxipeptidasas/genética , Genoma de los Insectos/genética , Animales , Bombyx/enzimología , Perfilación de la Expresión Génica , Familia de Multigenes , Filogenia , ARN Mensajero/genética , Reacción en Cadena en Tiempo Real de la Polimerasa , Reacción en Cadena de la Polimerasa de Transcriptasa InversaRESUMEN
The use of bioorthogonal probes that display fluorogenic or phosphorogenic properties is advantageous to the labeling and imaging of biomolecules in live cells and organisms. Herein we present the design of three iridium(III) complexes containing a nitrone moiety as novel phosphorogenic bioorthogonal probes. These probes were non-emissive owing to isomerization of the C=N group but showed significant emission enhancement upon cycloaddition reaction with strained cyclooctynes. Interestingly, the connection of the nitrone ligand to the cationic iridium(III) center led to accelerated reaction kinetics. These nitrone complexes were also identified as phosphorogenic bioorthogonal labels and imaging reagents for cyclooctyne-modified proteins. These findings contribute to the development of phosphorogenic bioorthogonal probes and imaging reagents.
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Iridio/química , Sondas Moleculares , Óxidos de Nitrógeno/química , Fósforo/químicaRESUMEN
The synthesis, characterization, photophysics, lipophilicity, and cellular properties of new phosphorescent ruthenium(II) polypyridine complexes functionalized with a dibenzocyclooctyne (DIBO) or amine moiety [Ru(N^N)2 (L)](PF6 )2 are reported (L=4-(13-N-(3,4:7,8-dibenzocyclooctyne-5-oxycarbonyl) amino-4,7,10-trioxa-tridecanyl-aminocarbonyl-oxy-methyl)-4'-methyl-2,2'-bipyridine bpy-DIBO, N^N=2,2'-bipyridine bpy (1 a), 1,10-phenanthroline phen (2 a); L=4-(13-amino-4,7,10-trioxa-tridecanylaminocarbonyl-oxy-methyl)-4'-methyl-2,2'-bipyridine bpy-NH2 , N^N=bpy (1 b), phen (2 b)). The strain-promoted alkyne-azide cycloaddition (SPAAC) reaction of the DIBO complexes 1 a and 2 a with benzyl azide were studied. Also, the DIBO complexes 1 a and 2 a can selectively label N-azidoglycans located on the surface of CHO-K1 and A549 cells that were pretreated with 1,3,4,6-tetra-O-acetyl-N-azidoacetyl-D-mannosamine (Ac4 ManNAz). Additionally, the intracellular trafficking and localization of these biomolecules were monitored using laser-scanning confocal microscopy. Interestingly, the biolabeling and cellular uptake efficiency of the DIBO complexes 1 a and 2 a were cell-line dependent, as revealed by flow cytometry and ICP-MS. Furthermore, the complexes showed good biocompatibility toward the Ac4 ManNAz-pretreated cells in the dark, but exhibited photoinduced cytotoxicity due to the generation of singlet oxygen.
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2,2'-Dipiridil/análogos & derivados , Alquinos/química , Derivados del Benceno/química , Membrana Celular/química , Sustancias Luminiscentes/química , Compuestos Organometálicos/química , Polisacáridos/análisis , 2,2'-Dipiridil/química , 2,2'-Dipiridil/toxicidad , Alquinos/toxicidad , Animales , Derivados del Benceno/toxicidad , Células CHO , Línea Celular , Cricetulus , Humanos , Sustancias Luminiscentes/toxicidad , Microscopía Confocal , Imagen Óptica , Compuestos Organometálicos/toxicidad , Coloración y EtiquetadoRESUMEN
BACKGROUND: Since it was first reported in 1935, Cucumber green mottle mosaic virus (CGMMV) has become a serious pathogen in a range of cucurbit crops. The virus is generally transmitted by propagation materials, and to date no effective chemical or cultural methods of control have been developed to combat its spread. The current study presents a preliminary analysis of the pathogenic mechanisms from the perspective of protein expression levels in an infected cucumber host, with the objective of elucidating the infection process and potential strategies to reduce both the economic and yield losses associated with CGMMV. METHODS: Isobaric tags for relative and absolute quantitation (iTRAQ) technology coupled with liquid chromatography-tandem mass spectrometric (LC-MS/MS) were used to identify the differentially expressed proteins in cucumber plants infected with CGMMV compared with mock-inoculated plants. The functions of the proteins were deduced by functional annotation and their involvement in metabolic processes explored by KEGG pathway analysis to identify their interactions during CGMMV infection, while their in vivo expression was further verified by qPCR. RESULTS: Infection by CGMMV altered both the expression level and absolute quantity of 38 proteins (fold change >0.6) in cucumber hosts. Of these, 23 were found to be up-regulated, while 15 were down-regulated. Gene ontology (GO) analysis revealed that 22 of the proteins had a combined function and were associated with molecular function (MF), biological process (BP) and cellular component (CC). Several other proteins had a dual function with 1, 7, and 2 proteins being associated with BP/CC, BP/MF, CC/MF, respectively. The remaining 3 proteins were only involved in MF. In addition, Kyoto Encyclopedia of Genes and Genomes (KEGG) analysis identified 18 proteins that were involved in 13 separate metabolic pathways. These pathways were subsequently merged to generate three network diagrams illustrating the interactions between the different pathways, while qPCR was used to track the changes in expression levels of the proteins identified at 3 time points during CGMMV infection. Taken together these results greatly expand our understanding of the relationships between CGMMV and cucumber hosts. CONCLUSIONS: The results of the study indicate that CGMMV infection significantly changes the physiology of cucumbers, affecting the expression levels of individual proteins as well as entire metabolic pathways. The bioinformatic analysis also identified several pathogenesis-related (PR) proteins that could be useful in the development of disease-resistant plants.
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Cucumis sativus/virología , Interacciones Huésped-Patógeno , Enfermedades de las Plantas/virología , Proteínas de Plantas/análisis , Proteoma/análisis , Tobamovirus/crecimiento & desarrollo , Cromatografía Liquida , Cucumis sativus/fisiología , Proteómica , Estrés Fisiológico , Espectrometría de Masas en TándemRESUMEN
In this Article, we present a series of cyclometalated iridium(III) polypyridine complexes of the formula [Ir(N^C)2(N^N)](PF6) that showed dual emission under ambient conditions. The structures of the cyclometalating and diimine ligands were changed systematically to investigate the effects of the substituents on the dual-emission properties of the complexes. On the basis of the photophysical data, the high-energy (HE) and low-energy (LE) emission features of the complexes were assigned to triplet intraligand ((3)IL) and triplet charge-transfer ((3)CT) excited states, respectively. Time-dependent density functional theory (TD-DFT) calculations supported these assignments and indicated that the dual emission resulted from the interruption of the communication between the higher-lying (3)IL and the lower-lying (3)CT states by a triplet amine-to-ligand charge-transfer ((3)NLCT) state. Also, the avidin-binding properties of the biotin complexes were studied by emission titrations, and the results showed that the dual-emissive complexes can be utilized as ratiometric probes for avidin. Additionally, all the complexes exhibited efficient cellular uptake by live HeLa cells. The MTT and Annexin V assays confirmed that no cell death and early apoptosis occurred during the cell imaging experiments. Interestingly, laser-scanning confocal microscopy revealed that the complexes were selectively localized on the cell membrane, mitochondria, or both, depending on the nature of the substituents of the ligands. The results of this work will contribute to the future development of dual-emissive transition metal complexes as ratiometric probes and organelle-selective bioimaging reagents.
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Colorantes Fluorescentes/química , Modelos Moleculares , Compuestos Organometálicos/química , Teoría Cuántica , Muerte Celular , Ciclización , Colorantes Fluorescentes/síntesis química , Células HeLa , Humanos , Iridio/química , Microscopía Confocal , Compuestos Organometálicos/farmacocinética , Piridinas/químicaRESUMEN
OBJECTIVE: To investigate the basic clinical characteristics and drug resistance of Haemophilus influenzae (Hi) infection in hospitalized children in the past two years. METHODS: A retrospective cross-sectional study was conducted to analyze Hi strains isolated from the sputum and pharyngeal swabs of children aged 0-17 years who were hospitalized in the Third People's Hospital of Chengdu between June 2011 and May 2013. RESULTS: A total of 117 strains were isolated from 111 hospitalized children. There were 102 cases (91.9%) of respiratory infection and 9 cases (8.1%) of other diseases. The positive rates of Hi in children with bronchopneumonia or pneumonia (50.8%, 30/59) and in children with acute laryngotracheobronchitis (50.0%, 2/4) were relatively high, followed by in children with capillary bronchitis (34.6%, 9/26), in children with acute bronchitis (24.2%, 32/132), in children with herpangina (19.0%, 4/21), in children with asthmatoid bronchitis (17.9%, 5/28), in children with acute upper respiratory tract infection (11.8%, 9/76), in children with acute tonsillitis (8.2%, 7/85), and in children with neonatal pneumonia (5.6%, 3/54). There were significant differences in the rates of resistance to amoxicillin-clavulanate (15% vs 23%; P=0.010) and chloramphenicol (25% vs 8%; P=0.015) between the two survey years. The frequencice of ß-lactamase-nonproducing-ampicillin-resistant (BLNAR) strains and ß-lactamase-producing-amoxicilli/clavulanate-resistant (BLPACR) strains increased from 12% to 21% and from 13% to 19% respectively during the two survey years (P>0.05). CONCLUSIONS: Hi plays an important role in the respiratory tract infection of children aged 0-17 years. The increasing trend of BLNAR and BLPACR rates makes it harder for antibiotic selection in clinical practice.
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Haemophilus influenzae/aislamiento & purificación , Adolescente , Combinación Amoxicilina-Clavulanato de Potasio/farmacología , Niño , Niño Hospitalizado , Preescolar , Estudios Transversales , Farmacorresistencia Bacteriana , Haemophilus influenzae/efectos de los fármacos , Humanos , Lactante , Recién Nacido , Estudios RetrospectivosRESUMEN
We report the development of a series of rhenium(I) polypyridine complexes appended with an electron-rich diaminoaromatic moiety as phosphorogenic sensors for nitric oxide (NO). The diamine complexes [Re(N^N)(CO)3 (py-DA)][PF6 ] (py-DA=3-(N-(2-amino-5-methoxyphenyl)aminomethyl)pyridine; N^N=1,10-phenanthroline (phen) (1 a), 3,4,7,8-tetramethyl-1,10-phenanthroline (Me4 -phen) (2 a), 4,7-diphenyl-1,10-phenanthroline (Ph2 -phen) (3 a)) have been synthesized and characterized. In contrast to common rhenium(I) diimines, these diamine complexes were very weakly emissive due to quenching of the triplet metal-to-ligand charge-transfer ((3) MLCT) emission by the diaminoaromatic moiety through photoinduced electron transfer (PET). Upon treatment with NO, the complexes were converted into the triazole derivatives [Re(N^N)(CO)3 (py-triazole)][PF6 ] (py-triazole=3-((6-methoxybenzotriazol-1-yl)methyl)pyridine; N^N=phen (1 b), Me4 -phen (2 b), Ph2 -phen (3 b)), resulting in significant emission enhancement (I/I0 ≈60). The diamine complexes exhibited high reaction selectivity to NO, and their emission intensity was found to be independent on pH. Also, these complexes were effectively internalized by HeLa cells and RAW264.7 macrophages with negligible cytotoxicity. Additionally, the use of complex 3 a as an intracellular phosphorogenic sensor for NO has been demonstrated.
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Diaminas/química , Óxido Nítrico/análisis , Compuestos Organometálicos/química , Piridinas/química , Renio/química , Animales , Diaminas/síntesis química , Diaminas/farmacocinética , Diaminas/farmacología , Células HeLa , Humanos , Macrófagos/efectos de los fármacos , Macrófagos/metabolismo , Ratones , Microscopía Confocal , Compuestos Organometálicos/síntesis química , Compuestos Organometálicos/farmacocinética , Compuestos Organometálicos/farmacología , Fenantrolinas/síntesis química , Fenantrolinas/química , Fenantrolinas/farmacocinética , Fenantrolinas/farmacología , Piridinas/síntesis química , Piridinas/farmacocinética , Piridinas/farmacologíaRESUMEN
BACKGROUND: Urinary infections are a common type of pediatric disease, and their treatment and prognosis are closely correlated with infection location. Common clinical manifestations and laboratory tests are insufficient to differentiate between acute pyelonephritis and lower urinary tract infection. This study was conducted to explore a diagnostic method for upper and lower urinary tract infection differentiation. METHODS: The diagnostic values of procalcitonin (PCT) and C-reactive protein (CRP) were analyzed using the receiver operating characteristic curve method for upper and lower urinary tract infection differentiation. PCT was determined using chemiluminescent immunoassay. RESULTS: The PCT and CRP values in children with acute pyelonephritis were significantly higher than those in children with lower urinary tract infection (3.90 ± 3.51 ng/ml and 68.17 ± 39.42 mg/l vs. 0.48 ± 0.39 ng/ml and 21.39 ± 14.92 mg/l). The PCT values were correlated with the degree of renal involvement, whereas the CRP values failed to show such a significant correlation. PCT had a sensitivity of 90.47% and a specificity of 88% in predicting nephropathia, whereas CRP had sensitivity of 85.71% and a specificity of 48%. CONCLUSIONS: Both PCT and CRP can be used for upper and lower urinary tract infection differentiation, but PCT has higher sensitivity and specificity in predicting pyelonephritis than CRP. PCT showed better results than CRP. PCT values were also correlated with the degree of renal involvement.
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Proteína C-Reactiva/análisis , Calcitonina/sangre , Precursores de Proteínas/sangre , Pielonefritis/sangre , Pielonefritis/diagnóstico , Infecciones Urinarias/sangre , Infecciones Urinarias/diagnóstico , Adolescente , Biomarcadores/sangre , Péptido Relacionado con Gen de Calcitonina , Preescolar , Femenino , Humanos , Lactante , Masculino , Reproducibilidad de los Resultados , Sensibilidad y EspecificidadRESUMEN
A series of phosphorescent cyclometalated iridium(III) polypyridine complexes appended with a ß-D-glucose moiety [Ir(N^C)2(bpy-TEG-ONCH3-ß-D-glc)](PF6) [bpy-TEG-ONCH3-ß-D-glc = 4-(10-N-methyl-N-(ß-D-glucopyranosyl)-amino-oxy-2,5,8-trioxa-dec-1-yl)-4'-methyl-2,2'-bipyridine; HN^C = 2-((1,1'-biphenyl)-4-yl)benzothiazole) (Hbt) (1a), 2-phenylpyridine (Hppy) (2a), 2-phenylquinoline (Hpq) (3a), 7,8-benzoquinoline (Hbzq) (4a)] has been synthesized and characterized. The D-galactose counterparts [Ir(N^C)2(bpy-TEG-ONCH3-ß-D-gal)](PF6) [bpy-TEG-ONCH3-ß-D-gal = 4-(10-N-methyl-N-(ß-D-galactopyranosyl)-amino-oxy-2,5,8-trioxa-dec-1-yl)-4'-methyl-2,2'-bipyridine; HN^C = Hbt (1b), Hppy (2b), Hpq (3b), Hbzq (4b)] and a sugar-free bt complex [Ir(bt)2(bpy-TEG-OMe)](PF6) [bpy-TEG-OMe = 4-(2,5,8,11-tetraoxa-dodec-1-yl)-4'-methyl-2,2'-bipyridine] (1c) have also been prepared. Upon photoexcitation, all the complexes displayed intense and long-lived triplet metal-to-ligand charge-transfer ((3)MLCT) [dπ(Ir) â π*(N^N)] or triplet intraligand ((3)IL) (π â π*) (N^C and N^N) emission. The lipophilicity, the cellular uptake efficiency, and cytotoxicity of the complexes toward human cervix epithelioid carcinoma cells (HeLa) have been examined. Temperature dependence and chemical inhibition experiments indicated that the transport of bt-glucose complex 1a across the cell membrane occurred through an energy-requiring process such as endocytosis, in additional to a pathway that was mediated by glucose transporters (GLUTs). Importantly, the cellular uptake efficiency of this complex was found to be strongly dependent on hormonal stimulation and inhibition, rendering it a new phosphorescent metabolic indicator. Additionally, laser-scanning confocal microscopy revealed that the complex was localized in the mitochondria and highly resistant to photobleaching compared to a fluorescent organic glucose derivative 2-(N-(7-nitrobenz-2-oxa-1,3-diazol-4-yl)amino)-2-deoxy-d-glucose (2-NBDG).
Asunto(s)
2,2'-Dipiridil/química , Complejos de Coordinación/química , Galactosa/química , Glucosa/química , Iridio/química , Sustancias Luminiscentes/química , 2,2'-Dipiridil/análisis , 2,2'-Dipiridil/metabolismo , Transporte Biológico , Complejos de Coordinación/análisis , Complejos de Coordinación/metabolismo , Endocitosis , Galactosa/análisis , Galactosa/metabolismo , Glucosa/análisis , Glucosa/metabolismo , Células HeLa , Humanos , Iridio/análisis , Iridio/metabolismo , Sustancias Luminiscentes/análisis , Sustancias Luminiscentes/metabolismoRESUMEN
We report herein the design, synthesis and characterisation of a series of luminescent iridium(III) porphyrin complexes [Ir(ttp)(CH2CH2OH)] (H2ttp = 5,10,15,20-tetra-4-tolylporphyrin) (1), [Ir(tpp-Ph-NO2)(CO)Cl] (H2tpp-Ph-NO2 = 5-(4-((4-nitrophenoxy)carbonyloxymethyl)phenyl)-10,15,20-triphenylporphyrin) (2), [Ir(tpp-COOMe)(Py)2](Cl) (H2tpp-COOMe = 5-(4-methoxycarbonylphenyl)-10,15,20-triphenylporphyrin; Py = pyridine) (3) and [Ir(tpp-COOH)(Py)2](Cl) (H2tpp-COOH = 5-(4-carboxylphenyl)-10,15,20-triphenylporphyrin) (4). All the complexes displayed long-lived near-infrared (NIR) emission attributed to an excited state of mixed triplet intraligand (3IL) (π â π*) (porphyrin) and triplet metal-to-ligand charge transfer (3MLCT) (dπ(Ir) â π*(porphyrin)) character. The cytotoxicity of the complexes toward HeLa cells was examined by the 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyltetrazolium bromide (MTT) assay. The cationic complexes 3 and 4 exhibited higher cytotoxic activity toward HeLa cells than their neutral counterparts 1 and 2. Cellular uptake studies by inductively coupled plasma-mass spectrometry (ICP-MS) and laser-scanning confocal microscopy (LSCM) indicated that complexes 3 and 4 showed higher cellular uptake efficiencies than complexes 1 and 2 due to their cationic charge, and they were enriched in the perinuclear region of the cells with negligible nuclear uptake. Additionally, the carboxyl complex 4 was used to label a model protein bovine serum albumin (BSA) via an amidation reaction. The resultant luminescent protein conjugate 4-BSA displayed similar photophysical properties and intracellular localisation behaviour to its parent complex. The results of this work will contribute to the development of luminescent iridium(III) porphyrin complexes and related bioconjugates as NIR-emissive probes for bioimaging applications.