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1.
ACS Omega ; 9(30): 32328-32349, 2024 Jul 30.
Artigo em Inglês | MEDLINE | ID: mdl-39100289

RESUMO

Nanoparticles play a crucial role in enhancing the thermal and rheological properties of nanofluids, making them a valuable option for increasing the efficiency of heat exchangers. This research explores how nanoparticle characteristics, such as concentration, size, and shape, impact the properties of nanofluids. Nanofluids' thermophysical properties and flow characteristics are essential in determining heat transfer efficiency and pressure loss. Nanoparticles with high thermal conductivity, such as metallic oxides like MgO, TiO2, and ZnO, can significantly improve the heat transfer efficiency by around 30% compared to the base fluid. The stability of nanofluids plays a crucial role in their usability. Various methods, such as adding surfactants, using ultrasonic mixing, and controlling pH, have been employed to enhance the stability of nanofluids. The desired thermophysical properties can be achieved by utilizing nanofluids to enhance the system's heat transfer efficiency. Modifying the size and shape of nanoparticles also considerably improves thermal conductivity, affecting nanofluid viscosity and density. Equations for determining heat transfer rate and pressure drop in a double-pipe heat exchanger are discussed in this review, emphasizing the significance of nanofluid thermal conductivity in influencing heat transfer efficiency and nanofluid viscosity in impacting pressure loss. This Review identifies a trend indicating that increasing nanoparticle volume concentration can enhance heat transfer efficiency to a certain extent. However, surpassing the optimal concentration can reduce Brownian motions due to higher viscosity and density. This Review offers a viable solution for enhancing the thermal performance of heat transfer equipment and serves as a fundamental resource for applying nanofluids in heat transfer applications.

2.
ACS Omega ; 9(30): 33033-33043, 2024 Jul 30.
Artigo em Inglês | MEDLINE | ID: mdl-39100344

RESUMO

Chronic diseases, notably cancer, pose a significant global threat to human life. Oncologists and medical professionals addressing malignancies confront challenges such as toxicity and multidrug resistance. To tackle these issues, the focus has shifted toward the employment of multifunctional colloidal gold nanoparticles. This study aims to design pH-sensitive doxorubicin-loaded gold nanoparticles using polyvinylpyrrolidone. The cytotoxic efficacy of the designed gold nanoarchitecture and its doxorubicin counterpart was assessed in an in vitro model using the HeLa cell. In comparison to the free drug, experimental evaluations showed that the gold nanoarchitecture outperformed significantly lower unspecific drug leaching and efficiently delivered the payload in a controlled manner, boosting the chemotherapy outcomes. This work opens a streamlined approach for engineering gold nanoarchitecture that could be further expanded to incorporate other therapeutics and/or functional moieties that require optimized controlled delivery, offering a one-size-fits-all solution and paving the revolutionary adjustments to healthcare procedures.

3.
Heliyon ; 10(15): e34895, 2024 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-39144920

RESUMO

This review describes the latest achievements in the development of encapsulated controlled-release fertilizers, which encompasses sustainability issues in agriculture. The research community's interest in this particular area of science has doubled over the last couple of years due to the yearly increasing complexity of the food and supply situation, as well as maintaining the development of modern society in the era of population outbreak. This review covers demand in timely systematization and comprehensive analysis of emerging research in so-called "smart fertilizers" that release mineral components in accordance with the needs for nutrients classified into controlled- and slow-release fertilizers (CRFs and SRFs). Along with the thoroughly selected fundamental studies published in this area, the review specially focuses on the materials-based classification, emphasizing the importance of the host matrix in the time-controlled release of dopant. This substantially differentiates our review and renders scientific novelty and relevancy to it. The review is divided into sections, dealing with the types of slow- and controlled-release fertilizers each, and supplemented with the critical view on their usage. All data regarding encapsulated fertilizers in this review are systematized for the convenience of the readership when becoming familiarized with the latest achievements in this area. Perspectives and potential pathways are also described to recommend and guide researchers working on the related academic fields.

4.
Nano Lett ; 24(20): 6148-6157, 2024 May 22.
Artigo em Inglês | MEDLINE | ID: mdl-38728265

RESUMO

Magnetic field mediated magnetic catalysts provide a powerful pathway for accelerating their sluggish kinetics toward the oxygen evolution reaction (OER) but remain great challenges in acidic media. The key obstacle comes from the production of an ordered magnetic domain catalyst in the harsh acidic OER. In this work, we form an induced local magnetic moment in the metallic Ir catalyst via the significant 3d-5d hybridization by introducing cobalt dopants. Interestingly, CoIr nanoclusters (NCs) exhibit an excellent magnetic field enhanced acidic OER activity, with the lowest overpotential of 220 mV at 10 mA cm-2 and s long-term stability of 120 h under a constant magnetic field (vs 260 mV/20 h without a magnetic field). The turnover frequency reaches 7.4 s-1 at 1.5 V (vs RHE), which is 3.0 times higher than that without magnetization. Density functional theory results show that CoIr NCs have a pronounced spin polarization intensity, which is preferable for OER enhancement.

5.
Int J Biol Macromol ; 266(Pt 2): 131338, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38569987

RESUMO

Development of nanoparticles (NPs) serving as contrast enhancing agents in MRI requires a combination of high contrasting effect with the biosafety and hemocompatibility. This work demonstrates that bovine serum albumin (BSA) molecules bound to paramagnetic Mn2+ ions are promising building blocks of such NPs. The desolvation-induced denaturation of BSA bound with Mn2+ ions followed by the glutaraldehyde-facilitated cross-linking provides the uniform in size 102.0 ± 0.7 nm BSA-based nanoparticles (BSA-NPs) loaded with Mn2+ ions, which are manifested in aqueous solutions as negatively charged spheres with high colloid stability. The optimal loading of Mn2+ ions into BSA-NPs provides maximum values of longitudinal and transverse relaxivity at 98.9 and 133.6 mM-1 s-1, respectively, which are among the best known from the literature. The spin trap EPR method indicates that Mn2+ ions bound to BSA-NPs exhibit poor catalytic activity in the Fenton-like reaction. On the contrary, the presence of BSA-NPs has an antioxidant effect by preventing the accumulation of hydroxyl radicals produced by H2O2. The NPs exhibit remarkably low hemolytic activity and hemagglutination can be avoided at concentrations lower than 110 µM. Thus, BSA-NPs bound with Mn2+ ions are promising candidates for combining high contrast effect with biosafety and hemocompatibility.


Assuntos
Manganês , Soroalbumina Bovina , Água , Soroalbumina Bovina/química , Manganês/química , Água/química , Animais , Prótons , Bovinos , Reagentes de Ligações Cruzadas/química , Nanopartículas/química , Hemólise/efeitos dos fármacos , Desnaturação Proteica/efeitos dos fármacos , Imageamento por Ressonância Magnética/métodos , Humanos
6.
Dalton Trans ; 53(19): 8417-8428, 2024 May 14.
Artigo em Inglês | MEDLINE | ID: mdl-38683378

RESUMO

To date, researchers in chase of economic cost-efficiency are faced with the problem of developing effective catalysts for water splitting without the use of platinoids. Herein, catalytic properties of hexanuclear rhenium cluster complexes are investigated in application to the hydrogen evolution reaction (HER). A paste composite electrode containing the cluster complexes was obtained, producing a current density of 10 mA cm-2 at an extraordinarily low overpotential of 90 mV (RHE). The {Re6Se8}-based complexes have shown very favorable reaction kinetics via 102 mV dec-1 value of the Tafel slope for HER reaction within the composition of the paste electrode. Model calculations of kinetic parameters using density functional theory also support the experimental findings. This work underscores the perspectivity of rhenium cluster compounds in HER and opens a promising avenue toward the practical implementation of hydrogen production through electrochemical water splitting.

7.
Nanomaterials (Basel) ; 13(8)2023 Apr 12.
Artigo em Inglês | MEDLINE | ID: mdl-37110936

RESUMO

In this study, Nickel oxide-based catalysts (NixOx) were synthesized and used for the in-situ upgrading process of heavy crude oil (viscosity 2157 mPa·s, and API gravity of 14.1° at 25 °C) in aquathermolysis conditions for viscosity reduction and heavy oil recovery. All characterizations of the obtained nanoparticles catalysts (NixOx) were performed through Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Atomic Force Microscopy (AFM), X-Ray and Diffraction (XRD), and ASAP 2400 analyzer from Micromeritics (USA), methods. Experiments of catalytic and non-catalytic upgrading processes were carried out in a discontinuous reactor at a temperature of 300 °C and 72 bars for 24 h and 2% of catalyst ratio to the total weight of heavy crude oil. XRD analysis revealed that the use of nanoparticles of NiO significantly participated in the upgrading processes (by desulfurization) where different activated form catalysts were observed, such as α-NiS, ß-NiS, Ni3S4, Ni9S8, and NiO. The results of viscosity analysis, elemental analysis, and 13C NMR analysis revealed that the viscosity of heavy crude oil decreased from 2157 to 800 mPa·s, heteroatoms removal from heavy oil ranged from S-4.28% to 3.32% and N-0.40% to 0.37%, and total content of fractions (ΣC8-C25) increased from 59.56% to a maximum of 72.21%, with catalyst-3 thank to isomerization of normal and cyclo-alkanes and dealkylation of lateral chains of aromatics structures, respectively. Moreover, the obtained nanoparticles showed good selectivity, promoting in-situ hydrogenation-dehydrogenation reactions, and hydrogen redistribution over carbons (H/C) is improved, ranging from 1.48 to a maximum of 1.77 in sample catalyst-3. On the other hand, the use of nanoparticle catalysts have also impacted the hydrogen production, where the H2/CO provided from the water gas shift reaction has increased. Nickel oxide catalysts have the potential for in-situ hydrothermal upgrading of heavy crude oil because of their great potential to catalyze the aquathermolysis reactions in the presence of steam.

8.
Nanomaterials (Basel) ; 13(3)2023 Jan 21.
Artigo em Inglês | MEDLINE | ID: mdl-36770399

RESUMO

The present work demonstrates the optimization of the ligand structure in the series of bis(phosphine oxide) and ß-ketophosphine oxide representatives for efficient coordination of Tb3+ and Eu3+ ions with the formation of the complexes exhibiting high Tb3+- and Eu3+-centered luminescence. The analysis of the stoichiometry and structure of the lanthanide complexes obtained using the XRD method reveals the great impact of the bridging group nature between two phosphine oxide moieties on the coordination mode of the ligands with Tb3+ and Eu3+ ions. The bridging imido-group facilitates the deprotonation of the imido- bis(phosphine oxide) ligand followed by the formation of tris-complexes. The spectral and PXRD analysis of the separated colloids indicates that the high stability of the tris-complexes provides their safe conversion into polystyrenesulfonate-stabilized colloids using the solvent exchange method. The red Eu3+-centered luminescence of the tris-complex exhibits the same specificity in the solutions and the colloids. The pronounced luminescent response on the antibiotic ceftriaxone allows for sensing the latter in aqueous solutions with an LOD value equal to 0.974 µM.

9.
Environ Res ; 217: 114672, 2023 01 15.
Artigo em Inglês | MEDLINE | ID: mdl-36356664

RESUMO

Photocatalytic dye degradation is a method of environmental degradation that is commonly used to eliminate various pollutants produced by pharmaceutical and textile industries. Herein, pure and chromium (Cr)-doped SnO2 nanoflakes were synthesized using a simple facile hydrothermal method and photocatalytic properties were studied under visible light illumination. In addition, photoelectrochemical (PEC) water oxidation properties were also studied using the prepared samples. Doping of transition metal ions introduces structural defects, which narrow the band gap of host sample, resulting in high catalytic activity. The synthesized doped SnO2 displayed a rutile tetragonal crystal phase with a nanoflakes-like surface morphology having no other contaminations. The optical band gap of Cr-doped SnO2 nanoflakes was significantly reduced (2.48 eV) over the pure sample (3.32 eV), due to successful incorporation of Cr ions into the host lattice. Furthermore, the dye removal efficiency of these nanoflakes was investigated for methyl orange (MO) and tetracycline (TC) organic contaminations. The Cr-doped SnO2 nanoflakes exhibited superior photodegradation with 87.8% and 90.6% dye removal efficiency, within 90 min of light illumination. PEC water oxidation analysis showed that the doped photoelectrode achieved enhanced photocurrent density and showed a higher photocurrent density (1.08 mA cm-2) over that of the undoped electrode (0.60 mA cm-2). Electrochemical impedance spectroscopy (EIS) showed that doped electrodes exhibited lesser charge resistance than the pure electrode. The synthesized Cr-doped SnO2 nanoflakes are suitable for water oxidation and photodegradation of organic pollutants. Thus, we strongly believe that the obtained results in this report will continue to provide new opportunities for the improvement of effective visible light photocatalysts for industrial wastewater treatment and water splitting for H2 generation.


Assuntos
Poluentes Ambientais , Água , Água/química , Cromo , Oxirredução , Luz
10.
Environ Res ; 217: 114923, 2023 01 15.
Artigo em Inglês | MEDLINE | ID: mdl-36435491

RESUMO

The worldwide energy calamity and ecological disturbances demand materials that can remove harmful contaminants from the polluted water. Recently, semiconductor-based catalytic dye removal has created much consideration due to its high efficacy and eco-friendly contaminated water treatment processes. Vanadium oxide (V2O5) has attracted superior attention as a catalyst due to its robust oxidation power, chemical inertness, and stability against photodegradation. In this study, pristine and cobalt (Co)-doped V2O5 samples were synthesized by solvothermal method and examined for their photo-degradation activity and photoelectrochemical (PEC) water oxidation properties. The orthorhombic crystal phase was confirmed by X-ray diffraction (XRD), hexagonal-shaped morphology was observed by scanning electron microscope (SEM) and reduced optical band gap (2.01 eV) was noticed for doped V2O5 catalyst compared to the pristine (2.20 eV) catalyst. The doped V2O5 catalyst exhibited enhanced photodegradation of crystal violet CV (92.7%) and Cr (VI) reduction (90.5%) after 100 min of light irradiation. The doped photocatalyst exhibited approximately 2.1 and 1.9-fold enhancement of photodegradation of CV and Cr(VI) reduction, respectively. The doped electrode showed improved photocurrent density (0.54 mA/cm-2) compared to pristine electrode (0.12 mA/cm-2). Moreover, the doped electrode showed reduced charge-transfer resistance and enhanced charge-transfer properties compared to those of the pristine electrode. Hence, the prepared hexagonal-shaped V2O5 is a suitable material for the elimination of environmental contaminants from the polluted water as well as water splitting for hydrogen generation.


Assuntos
Cobalto , Poluentes Ambientais , Oxirredução , Óxidos/química , Fotólise , Catálise
11.
Int J Mol Sci ; 23(22)2022 Nov 17.
Artigo em Inglês | MEDLINE | ID: mdl-36430721

RESUMO

A number of nickel complexes of sodium pectate with varied Ni2+ content have been synthesized and characterized. The presence of the proton conductivity, the possibility of the formation of a dense spatial network of transition metals in these coordination biopolymers, and the immobilization of transition ions in the catalytic sites of this class of compounds make them promising for proton-exchange membrane fuel cells. It has been established that the catalytic system composed of a coordination biopolymer with 20% substitution of sodium ions for divalent nickel ions, Ni (20%)-NaPG, is the leading catalyst in the series of 5, 15, 20, 25, 35% substituted pectates. Among the possible reasons for the improvement in performance the larger specific surface area of this sample compared to the other studied materials and the narrowest distribution of the vertical size of metal arrays were registered. The highest activity during CV and proximity to four-electron transfer during the catalytic cycle have also been observed for this compound.


Assuntos
Níquel , Prótons , Pectinas , Oxigênio
12.
Molecules ; 27(20)2022 Oct 11.
Artigo em Inglês | MEDLINE | ID: mdl-36296384

RESUMO

The present work introduces the series of thiacalix[4]arenes (H4L) bearing different upper-rim substituents (R = H, Br, NO2) for rational design of ligands providing an antenna-effect on the NIR Yb3+-centered luminescence of their Yb3+ complexes. The unusual inclusive self-assembly of H3L- (Br) through Brπ interactions is revealed through single-crystal XRD analysis. Thermodynamically favorable formation of dimeric complexes [2Yb3+:2HL3-] leads to efficient sensitizing of the Yb3+ luminescence for H4L (Br, NO2), while poor sensitizing is observed for ligand H4L (H). X-ray analysis of the single crystal separated from the basified DMF solutions of YbCl3 and H4L(NO2) has revealed the transformation of the dimeric complexes into [4Yb3+:2L4-] ones with a cubane-like cluster structure. The luminescence characteristics of the complexes in the solutions reveal the peculiar antenna effect of H4L(R = NO2), where the triplet level at 567 nm (17,637 cm-1) arisen from ILCT provides efficient sensitizing of the Yb3+ luminescence.

13.
Pharmaceutics ; 14(7)2022 Jul 20.
Artigo em Inglês | MEDLINE | ID: mdl-35890403

RESUMO

The present work introduces rational design of nanoparticulate Mn(II)-based contrast agents through both variation of the µ3 (inner) ligands within a series of hexarhenium cluster complexes [{Re6(µ3-Q)8}(CN)6]4- (Re6Q8, Q = S2-, Se2- or Te2-) and interfacial decoration of the nanoparticles (NPs) K4-2xMnxRe6Q8 (x = 1.3 - 1.8) by a series of pluronics (F-68, P-123, F-127). The results highlight an impact of the ligand and pluronic for the optimal colloid behavior of the NPs allowing high colloid stability in ambient conditions and efficient phase separation under the centrifugation. It has been revealed that the K4-2xMnxRe6Se8 NPs and those decorated by F-127 are optimal from the viewpoint of magnetic relaxivities r1 and r2 (8.9 and 10.9 mM-1s-1, respectively, at 0.47 T) and low hemoagglutination activity. The insignificant leaching of Mn2+ ions from the NPs correlates with their insignificant effect on the cell viability of both M-HeLa and Chang Liver cell lines. The T1- and T2-weighted contrast ability of F-127-K4-2xMnxRe6Q8 NPs was demonstrated through the measurements of phantoms at whole body 1.5 T scanner.

14.
Colloids Surf B Biointerfaces ; 217: 112664, 2022 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-35780611

RESUMO

The present work introduces self-assembled polystyrenesulfonate (PSS) molecules as soft nanocapsules for incorporation of Eu3+-Sm3+ complexes by the solvent exchange procedure. The high levels of Eu3+- and Sm3+-luminescence of the complexes derives from the ligand-to-metal energy transfer, in turn, resulted from the complex formation of Eu3+and Sm3+ ions with the three recently synthesized cyclophanic 1,3-diketones. The structural features of the ligands are optimized for the high thermal sensitivity of Eu3+- luminescence in DMF solutions. The PSS-nanocapsules (∼100 nm) provide both colloid and chemical stabilization of the ultrasmall (3-5 nm) nanoprecipitates of the complexes, although their luminescence spectra patterns and excited state lifetimes differ from the values measured for the complexes in DMF solutions. The specific concentration ratio of the Eu3+-Sm3+ complexes in the DMF solutions allows to tune the intensity ratio of the luminescence bands at 612 and 650 nm in the heterometallic Eu3+-Sm3+ colloids. The thermal sensitivity of the Eu3+- and Sm3+-luminescence of the complexes derives from the static quenching both in PSS-colloids and in DMF solutions, while the thermo-induced dynamic quenching of the luminescence is significant only in DMF solutions. The reversibility of thermo-induced luminescence changes of the Eu3+-Sm3+ colloids is demonstrated by six heating-cooling cycles. The DLS measurements before and after the six cycles reveal the invariance of the PSS-based capsule as the prerequisite for the recyclability of the temperature monitoring through the ratio of Eu3+-to- Sm3+ luminescence.


Assuntos
Luminescência , Nanocápsulas , Európio/química , Íons , Ligantes
15.
J Environ Manage ; 315: 115120, 2022 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-35490484

RESUMO

Novel g-C3N4 functionalized yttrium-doped ZrO2 hybrid heterostructured (g-YZr) nanoparticles have been synthesized to investigate photocatalytic Cr(VI) reduction as well as electrochemical energy storage applications. The nanoparticles have been characterized to examine their structural, optical, and photocatalytic properties. XRD confirmed the incorporation of dopant ions and heterostructure development between g-C3N4 and doped ZrO2. When g-C3N4 was doped with ZrO2, the ability of light adsorption was greatly enhanced due to the narrow band gap. The distinctive structure of g-YZr exhibited outstanding photocatalytic Cr(VI) reduction owing to its superior surface area, which greatly prevented the charge carriers' recombination rate and exhibited superior photocatalytic performance within 90 min of solar light irradiation. Furthermore, these catalysts demonstrated similar catalytic Cr(VI) reduction activity following four repeatability tests, indicating the exceptional structural stability of g-YZr catalysts. The electrochemical performance of the electrodes revealed that g-YZr exhibited superior specific capacitance over the other electrodes owing to extra energetic sites and robust synergic effect. Enhanced specific capacitance and long cyclic stability of the hybrid heterostructures displayed their usefulness for energy storage applications.

16.
Nanomaterials (Basel) ; 11(11)2021 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-34835844

RESUMO

The report introduces hybrid polyelectrolyte-stabilized colloids combining blue and green-emitting building blocks, which are citrate carbon dots (CDs) and [TbL]+ chelate complexes with 1,3-diketonate derivatives of calix[4]arene. The joint incorporation of green and blue-emitting blocks into the polysodium polystyrenesulfonate (PSS) aggregates is carried out through the solvent-exchange synthetic technique. The coordinative binding between Tb3+ centers and CD surface groups in initial DMF solutions both facilitates joint incorporation of [TbL]+ complexes and the CDs into the PSS-based nanobeads and affects fluorescence properties of [TbL]+ complexes and CDs, as well as their ability for temperature sensing. The variation of the synthetic conditions is represented herein as a tool for tuning the fluorescent response of the blue and green-emitting blocks upon heating and cooling. The revealed regularities enable developing either dual-band luminescent colloids for monitoring temperature changes within 25-50 °C through double color emission or transforming the colloids into ratiometric temperature sensors via simple concentration variation of [TbL]+ and CDs in the initial DMF solution. Novel hybrid carbon dots-terbium chelate PSS-based nanoplatform opens an avenue for a new generation of sensitive and customizable single excited dual-band nanothermometers.

17.
Molecules ; 26(5)2021 Feb 24.
Artigo em Inglês | MEDLINE | ID: mdl-33668373

RESUMO

The present review is aimed at highlighting outlooks for cyclophanic 1,3-diketones as a new type of versatile ligands and building blocks of the nanomaterial for sensing and bioimaging. Thus, the main synthetic routes for achieving the structural diversity of cyclophanic 1,3-diketones are discussed. The structural diversity is demonstrated by variation of both cyclophanic backbones (calix[4]arene, calix[4]resorcinarene and thiacalix[4]arene) and embedding of different substituents onto lower or upper macrocyclic rims. The structural features of the cyclophanic 1,3-diketones are correlated with their ability to form lanthanide complexes exhibiting both lanthanide-centered luminescence and magnetic relaxivity parameters convenient for contrast effect in magnetic resonance imaging (MRI). The revealed structure-property relationships and the applicability of facile one-pot transformation of the complexes to hydrophilic nanoparticles demonstrates the advantages of 1,3-diketone calix[4]arene ligands and their complexes in developing of nanomaterials for sensing and bioimaging.


Assuntos
Calixarenos/química , Complexos de Coordenação/química , Cetonas/química , Nanopartículas/química , Fenóis/química , Calixarenos/síntese química , Complexos de Coordenação/síntese química , Cetonas/síntese química , Ligantes , Estrutura Molecular , Tamanho da Partícula , Fenóis/síntese química , Propriedades de Superfície
18.
Sci Rep ; 10(1): 20541, 2020 11 25.
Artigo em Inglês | MEDLINE | ID: mdl-33239623

RESUMO

The work introduces hydrophilic PSS-[Tb2(TCAn)2] nanoparticles to be applied as highly sensitive intracellular temperature nanosensors. The nanoparticles are synthesized by solvent-induced nanoprecipitation of [Tb2(TCAn)2] complexes (TCAn - thiacalix[4]arenes bearing different upper-rim substituents: unsubstituted TCA1, tert-buthyl-substituted TCA2, di- and tetra-brominated TCA3 and TCA4) with the use of polystyrenesulfonate (PSS) as stabilizer. The temperature responsive luminescence behavior of PSS-[Tb2(TCAn)2] within 293-333 K range in water is modulated by reversible changes derived from the back energy transfer from metal to ligand (M* → T1) correlating with the energy gap between the triplet levels of ligands and resonant 5D4 level of Tb3+ ion. The lowering of the triplet level (T1) energies going from TCA1 and TCA2 to their brominated counterparts TCA3 and TCA4 facilitates the back energy transfer. The highest ever reported temperature sensitivity for intracellular temperature nanosensors is obtained for PSS-[Tb2(TCA4)2] (SI = 5.25% K-1), while PSS-[Tb2(TCA3)2] is characterized by a moderate one (SI = 2.96% K-1). The insignificant release of toxic Tb3+ ions from PSS-[Tb2(TCAn)2] within heating/cooling cycle and the low cytotoxicity of the colloids point to their applicability in intracellular temperature monitoring. The cell internalization of PSS-[Tb2(TCAn)2] (n = 3, 4) marks the cell cytoplasm by green Tb3+-luminescence, which exhibits detectable quenching when the cell samples are heated from 303 to 313 K. The colloids hold unprecedented potential for in vivo intracellular monitoring of temperature changes induced by hyperthermia or pathological processes in narrow range of physiological temperatures.

19.
Mater Sci Eng C Mater Biol Appl ; 105: 110057, 2019 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-31546380

RESUMO

The present work introduces ternary Ln(III) (Ln = Eu, Yb, Lu) complexes with thenoyltriflouro1,3-diketonate (TTA-) and phosphine oxide derivative (PhO) as building blocks for core-shell nanoparticles with both Eu(III)- or Yb(III)-centered luminescence and the dual Eu(III)-Yb(III)-centered luminescence. Solvent-mediated self-assembly of the complexes is presented herein as the procedure for formation of EuLu, EuYb and YbLu heterometallic or homometallic cores coated by hydrophilic polystyrenesulfonate-based shells. Steady state and time resolved Eu-centered luminescence in homolanthanide and heterolanthanide EuLu and EuYb cores is affected by Eu → Eu and Eu → Yb energy transfer due to a close proximity of the lanthanide blocks within the core of nanoparticles. The Eu → Yb energy transfer is highlighted to be the reason for the enhancement of the NIR Yb-centered luminescence. Efficient cellular uptake, low cytotoxicity towards normal and cancer cells, and sensing ability of EuYb nanoparticles on lomefloxacin additives via both red and NIR channels make them promising as cellular imaging agents and sensors.


Assuntos
Antineoplásicos , Citotoxinas , Európio , Luminescência , Nanopartículas Metálicas , Neoplasias , Itérbio , Antineoplásicos/química , Antineoplásicos/farmacologia , Citotoxinas/química , Citotoxinas/farmacologia , Európio/química , Európio/farmacologia , Células HeLa , Humanos , Nanopartículas Metálicas/química , Nanopartículas Metálicas/uso terapêutico , Neoplasias/diagnóstico por imagem , Neoplasias/tratamento farmacológico , Itérbio/farmacologia
20.
Int J Mol Sci ; 20(13)2019 Jun 27.
Artigo em Inglês | MEDLINE | ID: mdl-31252567

RESUMO

The low photostability of conventional organic dyes and the toxicity of cadmium-based luminescent quantum dots have prompted the development of novel probes for in vitro and in vivo labelling. Here, a new fluorescent lanthanide probe based on silica nanoparticles is fabricated and investigated for optically traceable in vitro translocator protein (TSPO) targeting. The targeting and detection of TSPO receptor, overexpressed in several pathological states, including neurodegenerative diseases and cancers, may provide valuable information for the early diagnosis and therapy of human disorders. Green fluorescent terbium(III)-calix[4]arene derivative complexes are encapsulated within silica nanoparticles and surface functionalized amine groups are conjugated with selective TSPO ligands based on a 2-phenylimidazo[1,2-a]pyridine acetamide structure containing derivatizable carboxylic groups. The photophysical properties of the terbium complex, promising for biological labelling, are demonstrated to be successfully conveyed to the realized nanoarchitectures. In addition, the high degree of biocompatibility, assessed by cell viability assay and the selectivity towards TSPO mitochondrial membrane receptors, proven by subcellular fractional studies, highlight targeting potential of this nanostructure for in vitro labelling of mitochondria.


Assuntos
Corantes Fluorescentes/química , Nanopartículas/química , Dióxido de Silício/química , Térbio/química , Calixarenos/química , Linhagem Celular Tumoral , Corantes Fluorescentes/farmacologia , Humanos , Ligantes , Fenóis/química , Ligação Proteica , Receptores de GABA/efeitos dos fármacos , Receptores de GABA/metabolismo
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