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1.
Chem Sci ; 10(35): 8246-8252, 2019 Sep 21.
Artigo em Inglês | MEDLINE | ID: mdl-31673325

RESUMO

Photothermal therapy in the second near-infrared window (NIR-II, 1000-1700 nm) exhibits a significant advantage over the first near-infrared window (NIR-I, 650-950 nm) in terms of both maximum permissible exposure (MPE) and penetration depth. However, the thus far reported NIR-II photothermal agents (PTAs) have been focused just on inorganic semiconducting and organic polymeric semiconducting nanoparticles. Herein a novel cruciform phthalocyanine pentad was designed, synthesized, and characterized for the first time. The water-soluble nanoparticles (Zn4-H2Pc/DP NPs) assembled from this single molecular material with the help of DSPE-PEG2000-OCH3 exhibit characteristic absorption in the NIR-II region at 1064 nm with a large extinction coefficient of 52 L g-1 cm-1, high photothermal conversion efficiency of 58.3%, and intense photoacoustic signal. Moreover, both in vitro and in vivo studies reveal the good biocompatibility and notable tumor ablation ability of Zn4-H2Pc/DP NPs under 1064 nm laser irradiation. Theoretical density functional theory calculations interpret the two-dimensional compressional wave energy-dissipation pathway over the broad saddle curved framework of the cruciform conjugated phthalocyanine pentad, rationalizing the efficient photothermal properties of corresponding Zn4-H2Pc/DP NPs in the NIR-II window.

2.
Chemistry ; 25(71): 16207-16213, 2019 Dec 18.
Artigo em Inglês | MEDLINE | ID: mdl-31602719

RESUMO

The functionalization of natural 1D architectures is dependent on hierarchically inner nanostructures. However, the artificial supramolecular nanofibers or nanotubes were rarely developed with complex inner structures. Inspired by a biomimetic strategy, single-molecule-diameter nanofibers of double-decker phthalocyanine (EuPc2) with compartmentalized internal space and fantastic electrochemical features were developed upon air/water interfacial assembly with poly-l-lysine. EuPc2/poly-l-lysine nanofibers can be electrochemical sensors both in water and the gas phase and have the best analytical performances for nitrite among all the porphyrins or phthalocyanines monomers and assemblies. Imbedding nitrite in compartments not only promotes the sensing but also changes the supramolecular chirality of nanofibers, and the morphological-dependent sensing properties of EuPc2 assemblies in water are different from that in the gas phase. These results suggest the unprecedented properties for diverse applications of artificial 1D architectures containing complex inner nanostructures.

3.
Onco Targets Ther ; 12: 6181-6189, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31496723

RESUMO

Background: Circular RNAs (circRNAs) have been considered as key regulators of cancer biology. However, the functional role of hsa_circ_0023404 in non-small cell lung cancer (NSCLC) and its regulatory mechanism are still almost unknown. Methods: The expression of hsa_circ_0023404, miR-217 and zinc finger E-box-binding homeobox 1 (ZEB1) was evaluated by quantitative real-time polymerase chain reaction. The role of hsa_circ_0023404 in NSCLC progression was determined using cell count kit-8 assay, transwell migration and invasion assay. Luciferase reporter assay was performed to assess the interaction of hsa_circ_0023404, miR-217 and ZEB1 in NSCLC cells. Results: The expression of hsa_circ_0023404 was upregulated in NSCLC tissues, as well as in NSCLC cell lines. High hsa_circ_0023404 expression predicted short overall survival in NSCLC. Functionally, knockdown of hsa_circ_0023404 inhibited the proliferation, migration and invasion of NSCLC cells. In the further molecular mechanism study, hsa_circ_0023404 was shown to interact with miR-217/ZEB1 axis to contribute to the growth of NSCLC cells. Conclusion: hsa_circ_0023404 promotes the proliferation, migration and invasion of NSCLC cells by regulating miR-217/ZEB1 axis, providing a fresh perspective on circRNAs in NSCLC development.

4.
Ultrason Sonochem ; 58: 104648, 2019 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-31450373

RESUMO

We report the preparation of a porous and hierarchical manganese(III) oxide tiny nanostructures (Mn2O3 TNS) by a simple sonochemical approach. The nanocatalyst was synthesized by a bath-type ultrasound washer (Honda Electronics, W-118T) at 700 W and 300 kHz frequency. The morphology and chemical composition of the nanocatalyst were characterized by X-rays diffractometry (XRD), transmission electron microscopy (TEM), energy dispersive x-rays (EDX), X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). The electrocatalytic activity (ECA) was monitored by detection of toxic antibiotic drug (chloramphenicol) under phosphate buffer (pH 7.0). A facile sonochemical route was employed to prepare Mn2O3 TNS modified electrode. The screen-printed carbon electrode (SPCE) modified with Mn2O3 TNS was fabricated and applied for the electrochemical determination of chloramphenicol. Compared with bare SPCE, Mn2O3 TNS modified SPCE showed highest current response towards chloramphenicol. Furthermore, the modified sensor exhibits with a sharp peak and two linear ranges by using DPV (i) 0.015-1.28 µM with the sensitivity of 4.167 µA µM-1 cm-2 and (ii) 1.35-566.3 µM with the sensitivity of 7.205 µA µM-1 cm-2. Notably, we achieved a very low-level detection limit of 4.26 nM for the DPV detection of chloramphenicol. Further, the superior practicability of the nanosheets modified sensor can be used for real time sensing of chloramphenicol with good recover ranges.


Assuntos
Cloranfenicol/análise , Análise de Alimentos/métodos , Limite de Detecção , Compostos de Manganês/química , Leite/química , Nanoestruturas/química , Óxidos/química , Ondas Ultrassônicas , Animais , Antibacterianos/análise , Antibacterianos/química , Catálise , Cloranfenicol/química , Eletroquímica , Contaminação de Alimentos/análise , Concentração de Íons de Hidrogênio , Cinética
5.
Inorg Chem ; 58(4): 2422-2429, 2019 Feb 18.
Artigo em Inglês | MEDLINE | ID: mdl-30721033

RESUMO

For the purpose of further exploring the effect of nonperipherally attached substituents on single-ion magnet (SIMs) performance, tetrasubstituted bis[1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninato]terbium double-deckers, in both the reduced form TbH[Pc(α-OC5H11)4]2 (1) and the neutral form Tb[Pc(α-OC5H11)4]2 (2), were prepared. Single-crystal X-ray diffraction analysis for 2 unambiguously demonstrates the pinwheellike molecular structure with C4 symmetry. Magnetic investigations of the two bis(phthalocyaninato)terbium double-deckers reveal their characteristic SIM nature. 2 exhibits SIM performance superior to that of 1, as revealed by the larger energy barrier of 466 K for the former species and 431 K for the latter species due to the presence of organic radical-f (radical-Tb) interactions. The enhanced SIM performance of 2 in comparison to 1 actually stems from the presence of radical-f interactions and an enhanced ligand field strength. The latter positive factor is indicated by the electrostatic potential around the terbium ion on the basis of density functional theory (DFT) calculations.

6.
Artigo em Inglês | MEDLINE | ID: mdl-30743073

RESUMO

A new Schiff base derivative fluorescence-colorimetric chemosensor 2-hydroxy-5-[(2-hydroxy-1-naphthyl)methylideneamino]benzoic acid (H3L), has been designed and synthesized. H3L displayed high selectivity and sensitivity for detecting Cr3+, Cu2+, Fe3+ and Al3+ ions in DMF/H2O (v/v = 1/1) solution. When Cr3+, Cu2+ or Fe3+ ions were added, the solution of H3L in DMF/H2O exhibited different color changes. While with the addition of Fe3+ or Al3+ ions, the solution of H3L in DMF/H2O displayed different fluorescence responses. The bonding modes and bonding ratios of H3L and metal ions were explored by the Job's plot, 1H NMR titration, and electrospray ionization mass spectrometry (ESI-MS). The detection limits of H3L with Cr3+, Cu2+, Fe3+and Al3+ ions were 3.37 × 10-7 M, 4.65 × 10-7 M, 3.58 × 10-7 M and 4.89 × 10-7 M, respectively.

7.
Oncol Lett ; 17(1): 1279-1291, 2019 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-30655896

RESUMO

Long non-coding RNAs (lncRNAs) have been generally considered to serve important roles in various types of cancer, including gastric cancer. However, a comprehensive understanding of lncRNAs in gastric cancer requires further study. The present study performed an in-depth study revealed 50 differently expressed lncRNAs. The changed cellular pathways and biological process in gastric cancer were determined. To further confirm the functions of the differently expressed lncRNAs, co-expression networks were constructed between the lncRNAs and mRNA; this lead to the identification of 6 modules, which participated in various cellular pathways. In addition, 2 lncRNAs were identified which were associated with clinical outcome. The biological analysis and experimental evidence suggested that LINC00982 inhibited, while LL22NC03-N14H11.1 promoted the proliferation of gastric cancer cells. These lncRNAs may be considered as potential prognostic factor in gastric cancer.

8.
Dalton Trans ; 48(5): 1586-1590, 2019 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-30607410

RESUMO

Reversibly switched reduced protonated and neutral unprotonated forms of chiral mixed (phthalocyaninato)(porphyrinato) double-decker compounds were achieved, and comparative investigation over their magnetic properties firstly discovered that the introduction of f-radical interaction has a negative impact on enhancing the performance of SMMs.

9.
Ultrason Sonochem ; 64: 104717, 2019 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-32062532

RESUMO

The ultrasound-assisted synthesis of a novel neodymium sesquioxide nanoparticles (Nd2O5 NPs) decorated graphene oxide (GO) nanocomposite under ultrasonic probe (Ultrasonic processor model-PR 1000; frequency-30 kHz; power of 100 W/cm2) has been reported. After then, SEM, TEM, XRD, EDX and electrochemical impedance spectroscopy characterized was analyzed using Nd2O5 NPs@GO nanomaterial. Furthermore, the nanomaterial modified GCE (glassy carbon electrode) shows excellent electrochemical sensing performance towards anti-cancer drug. Raloxifene is one of the important anti-cancer drug. Moreover, the fabricated electrochemical sensor has showed a wide linear range for raloxifene between 0.03 and 472.5 µM and nanomolar detection limit (18.43 nM). In addition, the Nd2O5 NPs@GO modified sensor has been applied to the determination of raloxifene in human blood and urine samples.

10.
Inorg Chem ; 57(19): 12347-12353, 2018 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-30230324

RESUMO

Both heteroleptic (phthalocyaninato)(hemiporphyrazinato) and homoleptic bis(hemiporphyrazinato) dysprosium double-decker complexes, Dy[H(Hp)2] (1) and Dy[H(Pc)(Hp)] (2) (H2Pc = metal-free phthalocyanine; H2Hp = metal-free hemiporphyrazine), were designed, synthesized, and structurally characterized. The dysprosium center in both double-deckers are octa-coordinated with a nearly ideal square-antiprismatic coordination geometry, which provides an increased molecular anisotropy for the dysprosium ion and ensures the strengthened magnetic properties of both single-ion magnets (SIMs) in terms of coordination geometry. Magnetic studies reveal that both double-deckers exhibit typical SIM behavior with a spin reversal energy barrier of 80.1 ± 6.3 K for 1 and 57.3 ± 3.8 K for 2 as well as the hysteresis loops emerging at 3 K. In particular, introduction of two Hp ligands with four pyridine nitrogen atoms coordinated with the dysprosium spin center endows Dy[H(Hp)2] (1) with the thus far highest energy barrier among the sandwich-type dysprosium SIMs with N4-macrocyclic ligands, revealing the potential applications of sandwich-type lanthanide complexes with Hp ligands in molecular-based information storage.

11.
Inorg Chem ; 57(18): 11537-11542, 2018 Sep 17.
Artigo em Inglês | MEDLINE | ID: mdl-30156839

RESUMO

Two-photon excitable fluorescent dyes with integrated functions of targeted imaging and photodynamic therapy (PDT) are highly desired for the development of cancer theranostic agents. Herein, fluorescence resonance energy transfer (FRET) dyads, AceDAN-H2Por-Lyso (1a) and AceDAN-ZnPor-Lyso (1b), were developed for two-photon excited (TPE) lysosome-targeted fluorescence imaging and PDT of cancer cells. Under one-photon or two-photon excitation, the AceDAN donor can effectively transfer the excited state energy to the porphyrin acceptor via high efficient FRET, leading to the generation of deep-red fluorescence and singlet oxygen for cell imaging and PDT, respectively. 1a and 1b exhibit high photocytotoxicity and low dark cytotoxicity, in addition to strong lysosomal targeting capability in living cells. By taking the advantages of the two-photon absorption properties of the AceDAN donor and the properly distributed S1 and T1 states of the porphyrin acceptor, the AceDAN-porphyrin dyads 1a and 1b have been successfully applied to TPE-fluorescence imaging for tracking the significant morphology changes of cancer cells under two-photon laser irradiation.


Assuntos
Diagnóstico por Imagem/métodos , Corantes Fluorescentes/síntese química , Lisossomos/metabolismo , Metaloporfirinas/química , Naftalenos/química , Fotoquimioterapia/métodos , Fótons , Porfirinas/química , Células A549 , Transferência Ressonante de Energia de Fluorescência , Corantes Fluorescentes/química , Humanos , Microscopia Confocal , Estrutura Molecular , Morfolinas/química
12.
Chemistry ; 24(32): 8066-8070, 2018 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-29683531

RESUMO

The non-peripherally substituted 1,4,8,11,15,18,22,25-octa(butoxy)-phthalocyanine-involved unsymmetrical heteroleptic bis(phthalocyaninato) terbium double-decker, Tb(Pc){H[Pc(α-OC4 H9 )8 ]} (Pc=unsubstituted phthalocyanine) (1), was revealed to exhibit typical single ion magnet (SIM) behavior with effective energy barrier, 180 K (125 cm-1 ), and blocking temperature, 2 K, due to the severe deviation of the terbium coordination polyhedron from square-antiprismatic geometry. Fabrication of this double-decker compound into the novel tetrakis(phthalocyaninato) terbium pseudo-quadruple-decker Na2 {Tb(Pc)[Pc(α-OC4 H9 )8 ]}2 (2) single molecule magnet (SMM) not only optimizes the coordination polyhedron of terbium ion towards the square-antiprismatic geometry and intensifies the coordination field strength, but more importantly significantly enhances the molecular magnetic anisotropy in the unsymmetrical bis(phthalocyaninato) double-decker unit, along with the change of the counter cation from H+ of 1 to Na+ of 2, leading to an significantly enhanced magnetic behavior with spin-reversal energy barrier, 528 K (367 cm-1 ), and blocking temperature, 25 K. The present result is surely helpful towards developing novel tetrapyrrole lanthanide SMMs through rational design and self-assembly from bis(tetrapyrrole) lanthanide single ion magnet (SIM) building block.

13.
Inorg Chem ; 56(23): 14533-14539, 2017 Dec 04.
Artigo em Inglês | MEDLINE | ID: mdl-29155567

RESUMO

Sensitive and selective detection of Pb2+ is a very worthwhile endeavor in terms of both human health and environmental protection, as the heavy metal is fairly ubiquitous and highly toxic. In this study, we designed phthalocyanine-porphyrin (Pc-Por) heterodyads, namely, H2Pc-α-ZnPor (1) and H2Pc-ß-ZnPor (2), by connecting a zinc(II) porphyrin moiety to the nonperipheral (α) or peripheral (ß) position of a metal-free phthalocyanine moiety. Upon excitation at the porphyrin Soret region (420 nm), both of the dyads exhibited not only a porphyrin emission (605 nm) but also a phthalocyanine emission (ca. 700 nm), indicating the occurrence of intramolecular fluorescence resonance energy transfer (FRET) processes from the porphyrin donor to the phthalocyanine acceptor. The dyads can selectively bind Pb2+ in the phthalocyanine core leading to a red shift of the phthalocyanine absorption and thus a decrease of spectral overlap between the porphyrin emission and phthalocyanine absorption, which in turn suppresses the intramolecular FRET. In addition, the binding of Pb2+ can highly quench the emission of phthalocyanine by heavy-metal ion effects. The synergistic coupled functions endow the dyads with remarkable ratiometric fluorescent responses at two distinct wavelengths (F605/F703 for 1 and F605/F700 for 2). The emission intensity ratio increased as a linear function to the concentration of Pb2+ in the range of 0-4.0 µM, whereas the detection limits were determined to be 3.4 × 10-9 and 2.2 × 10-8 M for 1 and 2, respectively. Furthermore, by comparative study of 1 and 2, the effects of distance and relative orientation between Pc and ZnPor fluorophores on the FRET efficiency and sensing performance were highlighted, which is helpful for further optimizing such FRET systems.

14.
Inorg Chem ; 56(22): 13889-13896, 2017 Nov 20.
Artigo em Inglês | MEDLINE | ID: mdl-29111697

RESUMO

Bulky and strong electron-donating dibutylamino groups were incorporated onto the peripheral positions of one of the two phthalocyanine ligands in the bis(phthalocyaninato) terbium complex, resulting in the isolation of heteroleptic double-decker (Pc)Tb{Pc[N(C4H9)2]8} {Pc = phthalocyaninate; Pc[N(C4H9)2]8 = 2,3,9,10,16,17,23,24-octakis(dibutylamino)phthalocyaninate} with the nature of an unsymmetrical molecular structure, a square-antiprismatic coordination geometry, an intensified coordination field strength, and the presence of organic radical-f interaction. As a total result of all these factors, this sandwich-type tetrapyrrole lanthanide single-ion magnet (SIM) exhibits an overall enhanced magnetic performance including a high blocking temperature (TB) of 30 K and large effective spin-reversal energy barrier of Ueff = 939 K, rendering it the best sandwich-type tetrapyrrole lanthanide SIM reported thus far.

15.
Chemistry ; 23(60): 15017-15021, 2017 Oct 26.
Artigo em Inglês | MEDLINE | ID: mdl-28929536

RESUMO

The largest phthalocyanine-porphyrin-fused pentameric molecular arrays have been synthesized and spectroscopically characterized. The saddled molecular conformation revealed for the pentamer by DFT-D3 calculation in combination with the bulky peripheral substituents precludes effective face-to-face π-π intermolecular interaction. As a consequence, intermolecular C-H⋅⋅⋅π interactions together with the ubiquitous dispersion force arrays help to self-assemble the representative metal-free pentameric molecules into the three-dimensional supramolecular structures with nanorod morphology in CHCl3 and n-butanol. Powder X-ray diffraction (XRD) analysis and selected area electron diffraction (SAED) disclose the gradually increased long range of molecular ordering in the nanorods along with the increase in the substrate temperature from 30, 40, 50, to 60 °C. This in turn results in an increase in the semiconductivity of the single nanorod in the same order from 9.4×10-9 to 3.8×10-8 , 7.6×10-7 , and 6.3×10-5  S m-1 .

16.
Inorg Chem ; 56(19): 11503-11512, 2017 Oct 02.
Artigo em Inglês | MEDLINE | ID: mdl-28901754

RESUMO

Two triple-decker dinuclear sandwich dysprosium complexes, which are represented as Dy2[Pc(OC5H11)8]2[Cor(FPh)3] (1) and Dy2[Pc(OC5H11)8]2[Cor(ClPh)3] (2), were synthesized and characterized by spectroscopic and electrochemical methods in nonaqueous media. Their electronic structures were also investigated on the basis of TD-DFT calculations. The sandwich triple-decker nature with the molecular conformation of [Pc(OC5H11)8]Dy[Cor(FPh)3]Dy[Pc(OC5H11)8] for compound 1 was unambiguously revealed by single-crystal X-ray diffraction analysis and showed each dyprosium ion to be octacoordinated by the isoindole and pyrrole nitrogen atoms of an outer phthalocyanine ring and the central corrole ring, respectively. In addition, the magnetic properties of both compounds have also been characterized for exploring the functionalities of these types of triple-decker complexes.

17.
Inorg Chem ; 56(14): 8223-8231, 2017 Jul 17.
Artigo em Inglês | MEDLINE | ID: mdl-28648063

RESUMO

A pair of 1,1'-binaphthalene-bridged bisporphyrins, (R)- and (S)-H1, were designed to examine their chiral discrimination abilities toward a range of model diamines by using UV-vis absorption, CD, and 1H NMR spectroscopy with the assistance of DFT molecular modeling. The spectroscopic titrations revealed that (R)-/(S)-H1 could encapsulate (R)-/(S)-DACH and (R)-/(S)-PPDA in the chiral bisporphyrin cavities, leading to the selective formation of sandwich-type 1:1 complexes via dual Zn-N coordination interactions. In particular, the chiral recognition energy (ΔΔG°) toward (R)-/(S)-DACH was evaluated to be -4.02 kJ mol-1. The binding processes afforded sensitive CD spectral changes in response to the stereostructure of chiral diamines. Remarkable enantiodiscrimination effects were also detected in the NMR titrations of (R)-/(S)-H1, in which the nonequivalent chemical shift (ΔΔδ) can reach up to 0.57 ppm for (R)-/(S)-DACH. However, due to the large steric effect, another chiral diamine ((R)-/(S)-DPEA) could not be sandwiched in the chiral bisporphyrin cavity; therefore, (R)-/(S)-DPEA could hardly be discriminated by (R)-/(S)-H1. The present results demonstrate a chiral bisporphyrin host with integrated CD and NMR chiral sensing functions and also highlight the binding-mode-dependent character of its enantiodiscrimination performance for different chiral guests.

18.
Chem Commun (Camb) ; 53(26): 3765-3768, 2017 Mar 28.
Artigo em Inglês | MEDLINE | ID: mdl-28304062

RESUMO

Two mixed (phthalocyaninato)(hemiporphyrazinato) and two homoleptic bis(hemiporphyrazinato) rare earth double-decker complexes have been synthesized and structurally characterized. The EPR and NMR results clarified the protonated nature of these sandwich double-deckers. Spectroscopic and theoretical calculation results clearly reveal the predominantly aromatic nature of the mixed ring sandwich double-deckers.

19.
Org Lett ; 19(3): 650-653, 2017 02 03.
Artigo em Inglês | MEDLINE | ID: mdl-28112522

RESUMO

By the acid-catalyzed [2 + 2] condensation, an unprecedented neo-N-confused phlorin (neo-NCphlorin 1) was successfully synthesized. By treating 1 with N-chlorosuccinimide, the corresponding chloro-substituted neo-NCphlorin (1-Cl) was obtained. The oxidization of 1 with FeCl3 afforded the neo-N-confused phlorinone (neo-NCphlorinone 2), which bears a relatively coplanar conformation, different from the highly distorted ones observed for 1 and 1-Cl. Notably, 2 shows striking long-wavelength absorption beyond 1300 nm upon addition of TBAF.

20.
Sci Rep ; 6: 28026, 2016 06 13.
Artigo em Inglês | MEDLINE | ID: mdl-27294871

RESUMO

Conventional conjugated systems are characteristic of only either inherent or induced chirality because of synthetic challenge in combination of chiral segment into the main chromophore. In this work, chiral binaphthyl segment is directly fused into the central chromophore of a subphthalocyanine skeleton, resulting in a novel type of chiral subphthalocyanine analogue (R/S)-1 of integrated inherent and induced chirality. Impressively, an obviously enhanced optical activity is discerned for (R/S)-1 molecules, and corresponding enhancement mechanism is elucidated in detail. The synthesis strategy based on rational molecular design will open the door towards fabrication of chiral materials with giant optical activity, which will have great potential in chiroptical devices.

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