RESUMEN
Novel BODIPY photosensitizers were developed for imaging-guided photodynamic therapy. The introduction of a strong electron donor to the BODIPY core through a phenyl linker combined with the twisted arrangement between the donor and the BODIPY acceptor is essential for reducing the energy gap between the lowest singlet excited state and the lowest triplet state (ΔEST ), leading to a significant enhancement in the intersystem crossing (ISC) of the BODIPYs. Remarkably, the BDP-5 with the smallest ΔEST (ca. 0.44â eV) exhibited excellent singlet oxygen generation capabilities in both organic and aqueous solutions. BDP-5 also displayed bright emission in the far-red/near-infrared region in the condensed states. More importantly, both inâ vitro and inâ vivo studies demonstrated that BDP-5 NPs displayed a high potential for photodynamic cancer therapy and bioimaging.
Asunto(s)
Compuestos de Boro/química , Compuestos de Boro/farmacología , Diseño de Fármacos , Imagen Molecular/métodos , Fotoquimioterapia/métodos , Fármacos Fotosensibilizantes/química , Fármacos Fotosensibilizantes/farmacología , Compuestos de Boro/uso terapéutico , Línea Celular Tumoral , Humanos , Fármacos Fotosensibilizantes/uso terapéuticoRESUMEN
A phenolphthalein-based colorimetric probe bearing a dinitrobenzene group is reported as a thiophenol (PhSH)-selective chemodosimeter. PhSH can react with chemodosimeter 1 to afford phenolphthalein. The addition of PhSH to the aqueous solution of 1 followed by a change in pH of the resulting solution to basic induces a selective color change from colorless to pink. Furthermore, using PhSH and base as inputs and color change of 1 by naked eye as an output, leads to the construction of an AND logic gate.
Asunto(s)
Colorimetría/métodos , Fenolftaleína/química , Fenoles/análisis , Compuestos de Sulfhidrilo/análisis , Concentración de Iones de Hidrógeno , Estructura Molecular , Fenolftaleína/análisis , Fenolftaleína/síntesis química , Fenoles/química , Compuestos de Sulfhidrilo/químicaRESUMEN
Due to the simplicity and low detection limit, especially the bioimaging ability for cells, fluorescence probes serve as unique detection methods. With the aid of molecular recognition and specific organic reactions, research on fluorescent imaging probes has blossomed during the last decade. Especially, reaction based fluorescent probes have been proven to be highly selective for specific analytes. This review highlights our recent progress on fluorescent imaging probes for biologically important species, such as biothiols, reactive oxygen species, reactive nitrogen species, metal ions including Zn(2+), Hg(2+), Cu(2+) and Au(3+), and anions including cyanide and adenosine triphosphate (ATP).
Asunto(s)
Colorantes Fluorescentes/química , Imagen Molecular/métodos , Animales , Humanos , Peróxido de Hidrógeno/química , Metales/química , Compuestos de Sulfhidrilo/químicaRESUMEN
The accumulation of mercury pollution in plants can induce severe injury to human beings. It is a great challenge to monitor ultra-low concentrations of mercury in complicated matrixes. In this study, we successfully developed a strategy via Hg2+-triggered naphthalene-based fluorescent probe 1, which formed excimer that subsequently emitted fluorescence for the successful detection of ultra-low concentrations of Hg2+. The coordination of N and S atoms with Hg2+ facilitated the formation of excimer from the naphthalene-conjugated planes that were in sufficiently close proximity. Suppression of CîN bond rotation also induced the chelation-enhanced fluorescence (CHEF) effect, and the cumulative result of these effects was obvious fluorescent enhancement. Compared with probe 2, the other key factor for detection of Hg2+ is that the electrons of the hydroxyl group can easily transfer to a naphthalene moiety, resulting in an augmented π-electron density that enhanced the π-π stacking of the naphthalene-conjugated excimer. After detailed spectral studies and mechanism discussions, it was realized that probe 1 was able to detect ultra-low concentrations of Hg2+ in PBS buffer solution. The detection limit was calculated to be 1.98 nM. On account of the excellent performances, the probe was successfully applied in monitoring Hg2+ in water and pea sprouts with the potential for application as an advanced warning of contamination.
Asunto(s)
Colorantes Fluorescentes , Mercurio , Mercurio/análisis , Colorantes Fluorescentes/química , Colorantes Fluorescentes/síntesis química , Naftalenos/química , Espectrometría de Fluorescencia , Límite de Detección , Iones/análisis , Iones/química , Estructura MolecularRESUMEN
Adenosine 5'-triphosphate (ATP), synthesized in mitochondria, is an energy molecule in all living things. ATP not only serves as an energy source for protein synthesis and muscle contraction, but also as an important indicator for various diseases, such as Parkinson's disease, cardiovascular disease, and others. Accordingly, detection and sensing of ATP, especially in mitochondria, are important. In this study, a unique ring-opening process of rhodamine was coupled to recognition of ATP via introduction of a thiourea moiety, which was further linked to a naphthalimide group. A strong fluorescent emission at â¼580â nm was accompanied by a color change from colorless to pink upon addition of ATP at pHâ 7.4. Fluorescent probe 1 successfully imaged mitochondrial ATP with a Pearson's coefficient of 0.8. In addition, green emission from the naphthalimide moiety at â¼530â nm was observed without any change upon addition of ATP. This emission can be considered equivalent to an internal standard to utilize probe 1 as a dual-channel probe for ATP. Furthermore, probe 1 showed negligible cytotoxicity based on MTT assays.
Asunto(s)
Naftalimidas , Tiourea , Adenosina Trifosfato/química , Adenosina Trifosfato/metabolismo , Colorantes Fluorescentes/química , Mitocondrias/metabolismo , Naftalimidas/química , Rodaminas/química , Espectrometría de Fluorescencia , Tiourea/química , Tiourea/farmacologíaRESUMEN
Glutathione (GSH) is known to play a key role in the modulation of the redox environment in N-methyl-d-aspartate (NMDA) receptors. Coumarin derivative 1 bearing cyanoacrylamide and ifenprodil moieties was synthesized and reported to monitor GSH near NMDA receptors. The cyanoacrylamide moiety allows probe 1 to monitor GSH reversibly at pH 7.4 and the ifenprodil group acts as a directing group for NMDA receptors. Two-photon fluorescence microscopy allows probe 1 to successfully sense endogenous GSH in neuronal cells and hippocampal tissues with excitation at 750 nm. Furthermore, the addition of H2O2 and GSH induced a decrease and an increase in fluorescence emission. Probe 1 can serve as a potential practical imaging tool to get important information on GSH in the brain.
Asunto(s)
N-Metilaspartato , Receptores de N-Metil-D-Aspartato , Cumarinas , Colorantes Fluorescentes , Glutatión/metabolismo , Peróxido de HidrógenoRESUMEN
In this paper, we report new rhodamine hydrazone derivatives bearing thiol and carboxylic acid groups as selective fluorescent and colorimetric chemosensors for Hg(2+). The ring-opening process of spirolactam enables the large fluorescent enhancement and colorimetric change upon the addition of Hg(2+). The sample containing Hg(2+) was mixed with one of the chemosensors in a microchannel where the sensor was examined using confocal laser scanning microscopy. A plot of the fluorescent intensities of both chemosensors versus the log concentration of Hg(2+) exhibited a linear response (r(2)=0.95) in the range of 1 nM-1 µM, and the detection limits were 1 nM and 4.2 nM, respectively. Both chemosensors also enable the visualization of Hg(2+) accumulated in the nematode Caenorhabditis elegans previously exposed to nanomolar concentrations of Hg(2+).
Asunto(s)
Colorimetría/métodos , Mercurio/análisis , Técnicas Analíticas Microfluídicas/métodos , Imagen Molecular/métodos , Péptidos Cíclicos/química , Rodaminas/química , Animales , Caenorhabditis elegans/química , Cristalografía por Rayos X , Colorantes Fluorescentes/química , Conformación Molecular , Péptidos Cíclicos/síntesis químicaRESUMEN
Three structurally similar compounds, , bearing a fluorescence chromophore to which are appended morpholine, thiomorpholine and methylpiperazine substituents, display opposite fluorescence responses to pH changes, in contrast to that observed for fluorescein; and have extremely high binding selectivity towards Ag(+) ions and show completely different fluorescent and colorimetric changes upon addition of Ag(+), and the differences are proposed to be associated with different binding modes of and to this metal ion.
Asunto(s)
Fluoresceína/análisis , Fluoresceína/química , Plata/análisis , Plata/química , Cationes , Colorimetría , Concentración de Iones de Hidrógeno , Estructura Molecular , Espectrometría de Fluorescencia , VolumetríaRESUMEN
The first examples of boronic acid-linked fluorescent and colorimetric chemosensors for copper ions are reported; the monoboronic acid-conjugated rhodamine probe displays a highly selective fluorescent enhancement with Cu2+ among the various metal ions whereas the fluorescence of the bisboronic acid-conjugated fluorescein probe is selectively quenched by Cu2+, probably by way of a PET mechanism.
Asunto(s)
Ácidos Borónicos/química , Cobre/química , Fluoresceínas/química , Colorantes Fluorescentes/química , Rodaminas/química , Animales , Ácidos Borónicos/síntesis química , Células Cultivadas , Fluoresceínas/síntesis química , Rodaminas/síntesis química , Espectrometría de Fluorescencia , Pez Cebra/fisiologíaRESUMEN
Fluorescent chemosensors for sensing chiral molecules have been actively studied in recent years. In the current study, we report a naphthoimidazolium-cholesterol derivative (NI-chol 1) as a fluorescence based chemosensor for chiral recognition, in which the naphthoimidazolium serves not only as a fluorophore but also as a recognition moiety for anions via imidazolium (C-H)+-anion binding and the cholesterol unit acts as a chiral barrier. In particular, NI-chol 1 displayed unique and distinct ratiometric changes with Boc-d-Phe, on the other hand, Boc-l-Phe induced a negligible change. Furthermore, a distinct downfield shift (from 9.64 ppm to 9.96 ppm) of the imidazolium C-H peak was observed for Boc-d-Phe (5 eq.) with severe broadening, which indicates strong ionic hydrogen bonding between the C-H proton and the carboxylate.
RESUMEN
A new fluorescent chemosensor based on the acridine-Zn(II) derivative effectively recognizes pyrophosphate and inorganic phosphate at pH 7.4. Acridine derivative 1 displayed a fluorescent quenching effect with pyrophosphate; on the other hand, a large fluorescent enhancement was observed with inorganic phosphate. [structure: see text].
Asunto(s)
Acridinas/química , Difosfatos/análisis , Compuestos Organometálicos/química , Fosfatos/análisis , Zinc/química , Cristalografía por Rayos X , Difosfatos/química , Fluorescencia , Concentración de Iones de Hidrógeno , Modelos Moleculares , Estructura Molecular , Compuestos Organometálicos/síntesis química , Fosfatos/química , Sensibilidad y Especificidad , Volumetría/métodosRESUMEN
Lead identification and optimization is always a challenge to the medicinal chemists in drug discovery. Numbers of simple to complex and smaller to bigger organic compounds are prepared to meet the screening purpose of biological targets. Conventional solution phase synthetic methodologies are lacking the speed to run along with the need of medicinally interesting compounds due to their long reaction time, tedious work-up and purification problems. Alternatively opted polymer-supported synthesis of combinatorial libraries has been emerged as a promising tool in generating large numbers of structurally diverse molecules in a manner rapid and parallel. Microwave-assisted solid/liquid phase combinatorial synthetic techniques have been proved efficient in reducing the reaction time from days & hours to minutes & seconds and more promisingly to produce improved yields with high purities. This review briefs about the theory behind microwave chemical technology and glimpses of recent advancements in its application on polymer supported combinatorial synthesis.
Asunto(s)
Técnicas Químicas Combinatorias/métodos , Microondas , Polímeros/química , Calefacción , Polímeros/síntesis química , Solventes/químicaRESUMEN
Hypertension remains one of the most unmet medical needs of this century. While many drugs are available for treating hypertension, efforts are still insufficient to find potent therapeutic agents since cause for hypertension in all patients is not the same. Angiotensin-converting enzyme inhibitors (ACEIs) have emerged as an important class of drugs in the treatment of hypertension, congestive heart failure (CHF), protenuric renal disease, myocardial infarction and stroke. This class of drugs blocks the conversion of angiotensin I to angiotensin II and prevents bradykinin breakdown. However, the lack of specificity of ACEIs leads to the frequent side effects like cough and angio-oedema. Recently developed, specific non-peptide and orally active angiotensin receptor blockers (ARBs) have become the prime therapeutics as they alone or co-administration with ACE inhibitors can control the renin angiotensin disorders. This review explores recent developments in the design, synthesis, and structural modifications of ACE inhibitors as well as angiotensin receptor blockers.
Asunto(s)
Antagonistas de Receptores de Angiotensina , Inhibidores de la Enzima Convertidora de Angiotensina/uso terapéutico , Antihipertensivos/uso terapéutico , Inhibidores de la Enzima Convertidora de Angiotensina/química , Inhibidores de la Enzima Convertidora de Angiotensina/farmacología , Antihipertensivos/química , Antihipertensivos/farmacología , Quimioterapia Combinada , Insuficiencia Cardíaca/tratamiento farmacológico , Humanos , Hipertensión/tratamiento farmacológicoRESUMEN
Liquid phase combinatorial synthesis (LPCS) of piperazinediones by the use of soluble polymer support is explored to generate libraries. Proline anchored polyethylene glycol monomethyl ether (PEG) underwent dipeptide formation with different Fmoc-amino acids in the presence of dicyclohexyl carbodiimide (DCC). Deprotection of Fmoc accompanied with the cleavage from polymer support with cyclization of dipeptide to piperazinediones offers a facile and effective way to prepare diverse combinatorial libraries. Excellent yields and purities were achieved by simple wash and precipitation method.
Asunto(s)
Concentración de Iones de Hidrógeno , Piperazinas/síntesis química , Aminoácidos/química , Técnicas Químicas Combinatorias , Ciclización , Diciclohexilcarbodiimida , Dipéptidos/síntesis química , Fluorenos/química , Indicadores y Reactivos , PolietilenglicolesRESUMEN
The design and development of new pyrene-based fluorescent probes, P-Hcy-1 and P-Hcy-2, which display selective fluorescence enhancements in response to homocysteine (Hcy), are described. The distinctly different fluorescence responses of P-Hcy-1 and P-Hcy-2 to Hcy vs. Cys are explained by theoretical calculations. Finally, the results of cell experiments show that these probes can be used to selectively detect Hcy in mammalian cells.
Asunto(s)
Diagnóstico por Imagen/métodos , Colorantes Fluorescentes/química , Homocisteína/química , Animales , Línea Celular , Fluorescencia , Células HeLa , HumanosAsunto(s)
Cobre/química , Colorantes Fluorescentes/química , Técnicas Analíticas Microfluídicas/instrumentación , Rodaminas/química , Transferrina/química , Cibernética , Diseño de Equipo , Concentración de Iones de Hidrógeno , Lógica , Técnicas Analíticas Microfluídicas/métodos , Sensibilidad y EspecificidadRESUMEN
The 4-propargylamino-1,8-naphthalimide based fluorescent probe 1 has been explored as a sensor for selective detection of Au(3+). 4-Amino-1,8-naphthalimides, that possess typical intramolecular charge transfer (ICT) electronic characteristics, have been widely used as versatile platforms for fluorescent probes. The newly designed probe 1 contains a propargylamine moiety at C-4 of the naphthalimide chromophore that reacts with Au(3+) to generate a product that has distinctly different electronic properties from 1. Specifically, the probe undergoes a remarkable change in its absorption spectrum upon addition of Au(3+) that is associated with a distinct color change from yellow to light pink. In addition, a blue shift of ca. 56 nm also takes place in the emission spectra of the probe. Consequently, 1 serves as a reaction-based sensor or so called chemodosimeter for Au(3+). Importantly, surfactants enhance the rate of reaction of 1 with Au(3+), thus, enhancing its use as a real time sensor. Finally, the results of studies probing its application to bioimaging of Au(3+) in live cells show that the probe 1 has a unique ability to sense Au(3+) in cells and, in particular, in lipid droplets within cells.
Asunto(s)
1-Naftilamina/análogos & derivados , Cationes/análisis , Colorantes Fluorescentes/química , Oro/análisis , Naftalimidas/química , Imagen Óptica/métodos , Quinolonas/química , 1-Naftilamina/química , Células 3T3-L1 , Adipocitos/citología , Animales , Técnicas Biosensibles/métodos , Células HeLa , Humanos , RatonesRESUMEN
Two new coumarin derivatives displayed highly selective "Off-On" fluorescence changes with pyrophosphate between various anions including ATP, ADP, AMP and inorganic phosphate in 100% aqueous solution.
Asunto(s)
Cumarinas/química , Difosfatos/análisis , Fluorescencia , Aminas/química , Técnicas de Laboratorio Clínico/normas , Cobre/química , Cristalografía por Rayos X , Difosfatos/química , Fosfatos , Ácidos Picolínicos/químicaRESUMEN
The first "Off-On" type fluorescent probe for Au3+ is reported, in which rhodamine-alkyne derivative displayed highly selective fluorescence enhancement and "naked-eye" detection upon the addition of Au3+ at pH 7.4.
Asunto(s)
Oro/análisis , Pargilina/análogos & derivados , Propilaminas/química , Alquinos , Cationes , Colorimetría , Ciclización , Colorantes Fluorescentes , Pargilina/química , RodaminasRESUMEN
A new fluorescein derivative 1 bearing a boronic acid group was investigated as a fluorescent chemosensor for F-. An off-on type fluorescence enhancement was observed by the blocking of the photoinduced electron transfer mechanism, which was induced by the interaction between fluoride and boronic acid moiety.