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1.
Biomed Mater ; 19(3)2024 Mar 28.
Artigo em Inglês | MEDLINE | ID: mdl-38545719

RESUMO

Laser hyperthermia therapy (HT) has emerged as a well-established method for treating cancer, yet it poses unique challenges in comprehending heat transfer dynamics within both healthy and cancerous tissues due to their intricate nature. This study investigates laser HT therapy as a promising avenue for addressing skin cancer. Employing two distinct near-infrared (NIR) laser beams at 980 nm, we analyze temperature variations within tumors, employing Pennes' bioheat transfer equation as our fundamental investigative framework. Furthermore, our study delves into the influence of Ytterbium nanoparticles (YbNPs) on predicting temperature distributions in healthy and cancerous skin tissues. Our findings reveal that the application of YbNPs using a Gaussian beam shape results in a notable maximum temperature increase of 5 °C within the tumor compared to nanoparticle-free heating. Similarly, utilizing a flat top beam alongside YbNPs induces a temperature rise of 3 °C. While this research provides valuable insights into utilizing YbNPs with a Gaussian laser beam configuration for skin cancer treatment, a more thorough understanding could be attained through additional details on experimental parameters such as setup, exposure duration, and specific implications for skin cancer therapy.


Assuntos
Hipertermia Induzida , Nanopartículas , Neoplasias Cutâneas , Humanos , Itérbio , Hipertermia Induzida/métodos , Neoplasias Cutâneas/terapia , Temperatura Alta , Simulação por Computador , Lasers , Modelos Biológicos
2.
Dalton Trans ; 53(9): 3980-3984, 2024 Feb 27.
Artigo em Inglês | MEDLINE | ID: mdl-38349065

RESUMO

Two new ytterbium coordination compounds Yb(HPTC)(H2O)2 (Yb1) and Yb(HPTC)(Phen) (Yb2) were obtained using 10-carboxyperylene-3,4,9-tricarboxylate ion (HPTC3-) as a sensitizer. Both coordination compounds exhibited intense NIR-II luminescence upon excitation in the visible range and formed stable suspensions with nanoparticles of 50-70 nm in size in an aqueous solution of sodium alginate. Both complexes demonstrated non-toxicity up to at least 25 mg L-1 in two cell cultures: cancer cells MCF7 and embryonic cells HEK293T - making them suitable for bioimaging. For both complexes, the accumulation in cells was directly measured and it was shown that the accumulation of Yb2 was the same for both cell types (0.51-0.52 πg per cell), while Yb1 demonstrated selective accumulation in cancer cells (0.04 πg per cell for HEK293T and 7.00 πg per cell for MCF7). Thus, Yb1 can also be proposed as a selective vis-excited NIR emitting bioprobe.


Assuntos
Nanopartículas , Itérbio , Humanos , Animais , Suínos , Luminescência , Células HEK293
3.
Eur J Nucl Med Mol Imaging ; 51(6): 1558-1573, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38270686

RESUMO

PURPOSE: Classical brachytherapy of solid malignant tumors is an invasive procedure which often results in an uneven dose distribution, while requiring surgical removal of sealed radioactive seed sources after a certain period of time. To circumvent these issues, we report the synthesis of intrinsically radiolabeled and gum Arabic glycoprotein functionalized [169Yb]Yb2O3 nanoseeds as a novel nanoscale brachytherapy agent, which could directly be administered via intratumoral injection for tumor therapy. METHODS: 169Yb (T½ = 32 days) was produced by neutron irradiation of enriched (15.2% in 168Yb) Yb2O3 target in a nuclear reactor, radiochemically converted to [169Yb]YbCl3 and used for nanoparticle (NP) synthesis. Intrinsically radiolabeled NP were synthesized by controlled hydrolysis of Yb3+ ions in gum Arabic glycoprotein medium. In vivo SPECT/CT imaging, autoradiography, and biodistribution studies were performed after intratumoral injection of radiolabeled NP in B16F10 tumor bearing C57BL/6 mice. Systematic tumor regression studies and histopathological analyses were performed to demonstrate therapeutic efficacy in the same mice model. RESULTS: The nanoformulation was a clear solution having high colloidal and radiochemical stability. Uniform distribution and retention of the radiolabeled nanoformulation in the tumor mass were observed via SPECT/CT imaging and autoradiography studies. In a tumor regression study, tumor growth was significantly arrested with different doses of radiolabeled NP compared to the control and the best treatment effect was observed with ~ 27.8 MBq dose. In histopathological analysis, loss of mitotic cells was apparent in tumor tissue of treated groups, whereas no significant damage in kidney, lungs, and liver tissue morphology was observed. CONCLUSIONS: These results hold promise for nanoscale brachytherapy to become a clinically practical treatment modality for unresectable solid cancers.


Assuntos
Braquiterapia , Itérbio , Animais , Braquiterapia/métodos , Camundongos , Itérbio/química , Distribuição Tecidual , Nanopartículas/química , Marcação por Isótopo , Tomografia Computadorizada com Tomografia Computadorizada de Emissão de Fóton Único , Camundongos Endogâmicos C57BL , Goma Arábica/química , Feminino , Glicoproteínas/química , Linhagem Celular Tumoral , Radioisótopos/química , Radioisótopos/uso terapêutico
4.
Talanta ; 271: 125723, 2024 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-38295442

RESUMO

Nanoparticle-enhanced laser-induced breakdown spectroscopy and Tag-LIBS are two approaches that have been shown to significantly enhance LIBS sensitivity and specificity. In an effort to combine both of these approaches, we have initiated a study on the effect of the presence of Silver nanoparticle concentrations on Europium (Eu) and Ytterbium (Yb) LIBS signals. These elements are part of metal-loaded polymers conjugated to antibodies. We observe a signal enhancement of the emission lines of about 10 and 12 times for the Europium and Ytterbium lines. This study shows that Europium and Ytterbium are enhanced differently; Europium shows enhancement for both neutral and ionized species while the Ytterbium shows enhancement only for ionized species. Additionally, we found that NPs at 0.1 mg/mL and 0.05 mg/mL achieved maximum enhancement for Eu and Yb, respectively. Based on our findings, the temperature and electron density of Eu and Yb are not significantly different for NPs concentrations, but the total signal intensity is significantly higher for optimum NP concentrations for both Eu and Yb.


Assuntos
Európio , Nanopartículas Metálicas , Európio/química , Itérbio/química , Nanopartículas Metálicas/química , Prata/química , Análise Espectral , Biomarcadores , Lasers
5.
Braz Dent J ; 34(4): 93-106, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37909646

RESUMO

Radiopaque properties in the infiltrant should be interesting for clinicians to feel more confident to indicate this treatment. Thus, the aim of this study was to evaluate the effect of the incorporation of barium and ytterbium particles on the physical properties of resin infiltrants. Groups were divided according to the addition of ytterbium oxide (Y) alone (30 or 40%) or Y with barium (YB) (15/15% or 20/20% respectively) in the Icon commercial infiltrant and in the experimental infiltrant base. Digital radiography (n=5), Microradiography (n=5), Microtomography (n=3), degree of conversion (n=5), water sorption (n=16), solubility (n=16), contact angle (n=16), flexural strength (n=16), elastic modulus (n=16) and Energy dispersive X-ray Spectroscopy (n=10) were performed. Analyses were performed using the R program, with a significance level of 5%, and microradiography and Microtomography analyses were evaluated qualitatively. In groups with 30 or 40% of ytterbium, radiopacity was higher or equal to enamel. Microradiography and Microtomography appear to have more radiopacity in groups with 40% (Y). Among the groups with no particle addition, those of the experimental infiltrant presented a higher degree of conversion than those of Icon®. In most groups, there was solubility below the ISO-recommended levels. The addition of particles resulted in higher viscosity. Groups with Icon had higher flexural strength and elastic modulus than groups with experimental infiltrant. The addition of 40% (Y) improved polymerization, had low solubility, and had greater radiopacity than enamel, however negatively affected the viscosity increasing then. Experimental groups with the base showed a higher water sorption than Icon groups.


Assuntos
Resinas Compostas , Itérbio , Resinas Compostas/química , Bário , Itérbio/química , Ácidos Polimetacrílicos/química , Teste de Materiais , Água
6.
Comput Biol Chem ; 106: 107930, 2023 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-37542846

RESUMO

In this study, the one-pot synthetic methodology for the preparation of substituted pyrroles with diethyl acetylene-dicarboxylate is reported for the various pyrrole derivatives via the Trifimow synthesis process from oximes. This method also offers the literature as a cyclization pathway using a ytterbium triflate catalyst. Another importance of this study is the use of pyrrole derivatives in pharmaceuticals, biological processes, and agrochemicals. From this point of view, the development of a new catalyst in synthetic organic chemistry and the difference in the method is also important. The syntheses of the target substituted pyrroles are accomplished in high yields. Also, all synthesized structures were confirmed by 1H NMR, 13C NMR, and IR spectra. The DFT computations were leveraged for structural and spectroscopic validation of the compounds. Then, FMO and NBO analyses were subsequently employed to elucidate the reactivity characteristics and intramolecular interactions within these compounds. Also, ADMET indices were ascertained to assess potential pharmacokinetic properties, drug-like qualities, and possible adverse effects of these compounds. Last, optimized molecules were analyzed by molecular docking methods against crystal structures of Bovine Serum Albumin and Leukemia Inhibitory Factor, and their binding affinities, interaction details, and inhibition constants were determined.


Assuntos
Pirróis , Itérbio , Simulação de Acoplamento Molecular , Pirróis/química , Catálise , Estrutura Molecular
7.
Acta Biomater ; 168: 628-636, 2023 09 15.
Artigo em Inglês | MEDLINE | ID: mdl-37454706

RESUMO

The development of functional biomaterials with real-time monitoring of mineralization processes, drug release and biodistribution has potential applications but remains an unsolved challenge. Herein, erbium- and ytterbium- containing mesoporous bioactive glass microspheres (MBGs:Er/Yb) with blue and red emission at an excitation wavelength of 980 nm were synthesized by a sol-gel combined with organic template method. As the concentration of Yb3+ ions gradually increases, the emission intensity of the MBGs:Er/Yb exhibits a clear concentration quenching effect. Combined with in vitro bioactivity tests, the optimal molar ratio of Er3+/Yb3+ was determined to be 4:3. Therefore, MBGs:4Er/3Yb was selected for in vitro biomineralization and drug release monitoring. The results of biomineralization monitoring show that the upconversion luminescence intensity is closely related to the degree of biomineralization. The upconversion luminescence intensity of MBGs:4Er/3Yb is quenched with the increase of the degree of biomineralization. The degree of luminescence quenching during biomineralization can be semiquantized. Drug release monitoring experiments showed that the anticancer drug doxorubicin hydrochloride (DOX) was successfully loaded into MBGs:4Er/3Yb and selectively quenched the green emission. When DOX was released, the green emission recovered stably, and It/I0 increased gradually. Moreover, there was a linear relationship between It/I0 and cumulative drug release, indicating that DOX-MBGs:4Er/3Yb is highly sensitive to DOX release, and monitoring the It/I0 values of DOX-MBGs:4Er/3Yb can achieve real-time tracking of the DOX release process to a certain extent. In conclusion, MBGs:4Er/3Yb has potential application as an upconversion luminescence biomonitoring material in the field of bone tissue engineering. STATEMENT OF SIGNIFICANCE: Mesoporous bioactive glasses have great potential for applications in bone tissue repair due to their excellent biological properties, but the effective information of the repair process cannot be grasped in a timely manner. Therefore, real-time monitoring of mineralization and drug release processes will be beneficial to obtain the degree of healing and optimize the amount and distribution of drugs to improve targeted therapeutic effects. For biomaterials, in vitro biological properties determine their biological properties in vivo, where the environment is more complex and diverse, and thus in vitro biomonitoring is particularly crucial. The organic combination of physical properties and biological properties will also provide a feasible idea for the development of biomaterials.


Assuntos
Érbio , Itérbio , Luminescência , Microesferas , Liberação Controlada de Fármacos , Biomineralização , Distribuição Tecidual , Engenharia Tecidual , Materiais Biocompatíveis , Vidro
8.
Opt Lett ; 48(14): 3817-3820, 2023 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-37450758

RESUMO

A single-frequency distributed-Bragg-reflector fiber laser at 980 nm with a quantum defect of less than 0.6% was developed with a 1.5-cm 12 wt% ytterbium-doped phosphate fiber pumped by a 974.5-nm laser diode. Linearly polarized single-longitude-mode laser with a polarization extinction ratio (PER) of nearly 30 dB and spectral linewidth of less than 1.8 kHz was obtained. A maximum output power of 275 mW was measured at a launched pump power of 620 mW. The performance of the single-frequency fiber laser pumped at 909 nm and 976 nm was also characterized. This research demonstrated an approach to high-power single-frequency fiber laser oscillators with mitigated thermal effects.


Assuntos
Lasers Semicondutores , Itérbio
9.
ACS Biomater Sci Eng ; 9(8): 4607-4618, 2023 08 14.
Artigo em Inglês | MEDLINE | ID: mdl-37452737

RESUMO

Recently, various nanomaterials based on hydroxyapatite (HAp) have been developed for bioimaging applications. In particular, HAp doped with rare-earth elements has attracted significant attention, owing to its enhanced bioactivity and imaging properties. In this study, the wet precipitation method was used to synthesize HAp codoped with Yb and Gd. The synthesized Ybx-Gdx-HAp nanoparticles (NPs) were characterized via various techniques to analyze the crystal phase, functional groups, thermal characteristics, and particularly, the larger surface area. The IR783 fluorescence dye and a folic acid (FA) receptor were conjugated with the synthesized Ybx-Gdx-HAp NPs to develop an effective imaging contrast agent. The developed FA/IR783/Yb-Gd-HAp nanomaterial exhibited improved contrast, sensitivity, and tumor-specific properties, as demonstrated by using the customized LUX 4.0 fluorescence imaging system. An in vitro cytotoxicity study was performed to verify the biocompatibility of the synthesized NPs using MTT assay and fluorescence staining. Photodynamic therapy (PDT) was also applied to determine the photosensitizer properties of the synthesized Ybx-Gdx-HAp NPs. Further, reactive oxygen species generation was confirmed by Prussian blue decay and a 2',7'-dichlorofluorescin diacetate study. Moreover, MDA-MB-231 breast cancer cells were used to evaluate the efficiency of Ybx-Gdx-HAp NP-supported PDT.


Assuntos
Nanopartículas Metálicas , Itérbio/química , Gadolínio/química , Durapatita/química , Meios de Contraste/química , Nanopartículas Metálicas/química , Humanos , Neoplasias da Mama/diagnóstico por imagem , Neoplasias da Mama/terapia
10.
Opt Lett ; 48(13): 3447-3450, 2023 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-37390152

RESUMO

Erbium-ion-doped lithium niobate (LN) microcavity lasers working in the communication band have attracted extensive attention recently. However, their conversion efficiencies and laser thresholds still have significant room to improve. Here, we prepared microdisk cavities based on erbium-ytterbium-co-doped LN thin film by using ultraviolet lithography, argon ion etching, and a chemical-mechanical polishing process. Benefiting from the erbium-ytterbium co-doping-induced gain coefficient improvement, laser emission with an ultralow threshold (∼1 µW) and high conversion efficiency (1.8 × 10-3%) was observed in the fabricated microdisks under a 980-nm-band optical pump. This study provides an effective reference for improving the performance of LN thin-film lasers.


Assuntos
Érbio , Itérbio , Óxidos , Impressão
11.
Sci Rep ; 13(1): 9857, 2023 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-37330574

RESUMO

We explore the rich nature of correlations in the ground state of ultracold atoms trapped in state-dependent optical lattices. In particular, we consider interacting fermionic ytterbium or strontium atoms, realizing a two-orbital Hubbard model with two spin components. We analyze the model in one-dimensional setting with the experimentally relevant hierarchy of tunneling and interaction amplitudes by means of exact diagonalization and matrix product states approaches, and study the correlation functions in density, spin, and orbital sectors as functions of variable densities of atoms in the ground and metastable excited states. We show that in certain ranges of densities these atomic systems demonstrate strong density-wave, ferro- and antiferromagnetic, as well as antiferroorbital correlations.


Assuntos
Planeta Terra , Estrôncio , Itérbio
12.
Sensors (Basel) ; 23(11)2023 May 27.
Artigo em Inglês | MEDLINE | ID: mdl-37299855

RESUMO

A tunable and narrow-bandwidth Q-switched ytterbium-doped fiber (YDF) laser is investigated in this paper. The non-pumped YDF acts as a saturable absorber and, together with a Sagnac loop mirror, provides a dynamic spectral-filtering grating to achieve a narrow-linewidth Q-switched output. By adjusting an etalon-based tunable fiber filter, a tunable wavelength from 1027 nm to 1033 nm is obtained. When the pump power is 1.75 W, the Q-switched laser pulses with a pulse energy of 10.45 nJ, and a repetition frequency of 11.98 kHz and spectral linewidth of 112 MHz are obtained. This work paves the way for the generation narrow-linewidth Q-switched lasers with tunable wavelengths in conventional ytterbium, erbium, and thulium fiber bands to address critical applications such as coherent detection, biomedicine, and nonlinear frequency conversion.


Assuntos
Lasers , Itérbio , Desenho de Equipamento , Luz , Érbio
13.
Molecules ; 28(4)2023 Feb 08.
Artigo em Inglês | MEDLINE | ID: mdl-36838619

RESUMO

The luminescent performances of near-infrared (NIR) lanthanide (Ln) complexes were restricted greatly by vibration quenching of X-H (X = C, N, O) oscillators, which are usually contained in ligands and solvents. Encapsulating Ln3+ into a cavity of coordination atoms is a feasible method of alleviating this quenching effect. In this work, a novel ytterbium complex [Yb(DPPDA)2](DIPEA) coordinated with 4,7-diphenyl-1,10-phenanthroline-2,9-dicarboxylic acid (DPPDA) was synthesized and characterized by FT-IR, ESI-MS and elemental analysis. Under the excitation of 335 nm light, [Yb(DPPDA)2](DIPEA) showed two emission peaks at 975 and 1011 nm, respectively, which were assigned to the characteristic 2F5/2 → 2F7/2 transition of Yb3+. Meanwhile, this ytterbium complex exhibited a plausible absolute quantum yield of 0.46% and a luminescent lifetime of 105 µs in CD3OD solution. In particular, its intrinsic quantum yield was calculated to be 12.5%, and this considerably high value was attributed to the near-zero solvent molecules bound to Yb3+ and the absence of X-H oscillators in the first coordination sphere. Based on experimental results, we further proposed that the sensitized luminescence of [Yb(DPPDA)2](DIPEA) occurred via an internal redox mechanism instead of an energy transfer process.


Assuntos
Elementos da Série dos Lantanídeos , Itérbio , Espectroscopia de Infravermelho com Transformada de Fourier , Luminescência , Solventes
14.
Mol Divers ; 27(1): 511-515, 2023 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-35416620

RESUMO

A new Lewis acid promoted domino isocyanide insertion/5-exo-dig cyclization of readily available Strecker 3-component adducts to 4-substituted 5-aminoimidazole derivatives is herein reported. Despite their potential as relevant heterocyclic scaffolds in medicinal chemistry programs, this class of compounds is still underrepresented, with current synthetic strategies poorly efficient in terms of timing and yields. To this end, we show how the exploitation of unconventional reactivities of isocyanides, promoted by ytterbium-triflate, could represent a key resource to enable a fast and easy access to such an unexplored area of the chemical space.


Assuntos
Cianetos , Itérbio , Ciclização , Cianetos/química , Imidazóis/química
15.
Sensors (Basel) ; 22(23)2022 Nov 26.
Artigo em Inglês | MEDLINE | ID: mdl-36501899

RESUMO

We report an ytterbium (Yb) doped fiber Mach Zehnder interferometer (MZI) based on the up-taper fiber structure in a fiber ring laser (FRL) cavity. Different from the traditional FRL sensing system, in which additional filters are required, the designed structure simultaneously acts as a filter, sensor and gain medium. Furthermore, thanks to the high thermal-optical coefficient of Yb doped fiber, the temperature sensitivity of 0.261 nm/°C can be achieved in the range of 10-50 °C. In addition, benefiting from the unique characteristics of the laser system itself, the designed structure has a narrower linewidth (-0.2 nm) and a higher signal-to-noise ratio (SNR) (-40 dB) than the sensor system based on a broadband light source (BBS). Meanwhile, the refractive index (RI) response and stability of the system are measured. The RI sensitivity is up to 151 nm/RIU, and the wavelength fluctuation range within two hours is less than 0.2 nm. Therefore, the designed structure is expected to play a significant role in human life safety monitoring, aircraft engine temperature monitoring, etc.


Assuntos
Tecnologia de Fibra Óptica , Interferometria , Humanos , Itérbio , Refratometria , Lasers
16.
Inorg Chem ; 61(51): 20860-20865, 2022 Dec 26.
Artigo em Inglês | MEDLINE | ID: mdl-36493422

RESUMO

An interesting 48-metal Zn(II)-Yb(III) nanocluster (1) with a size of about 1.3 × 2.8 × 3.1 nm was constructed by carbonate templates from a Schiff base ligand. It exhibits ligand-centered emission and near-infrared (NIR) luminescence of Yb(III), which are used in the dual-emissive detection of rutin (Rut) with high sensitivity even in the presence of other interferences. The response behavior can be expressed by the second-order equation I980 nm/I510 nm = A*[Rut]2 + B*[Rut] + C, and the limits of detection to Rut for the emissions of 1 are 2.23 µM and 0.20 nM.


Assuntos
Elementos da Série dos Lantanídeos , Luminescência , Ligantes , Itérbio , Zinco
17.
Methods Appl Fluoresc ; 11(1)2022 Nov 16.
Artigo em Inglês | MEDLINE | ID: mdl-36380609

RESUMO

The Er3+/Yb3+doped La2O3phosphor samples were synthesized by the combustion method and then photoluminescence and photoacoustic spectroscopic studies were done. Prepared samples were annealed at 800 °C, 1000 °C and 1300 °C and all samples were found in pure hexagonal phase as confirmed by XRD analysis. From FE-SEM images it is found that particle size increases with increase in annealing temperature. The frequency upconversion emission spectra of samples were recorded by exciting the sample with 980 nm diode laser and maximum emission intensity is obtained for the sample annealed at 1000 °C for 2 h. A photoacoustic cell was designed and wavelength dependent photoacoustic spectra were measured. The effect of sample storage time on radiative and non-radiative emission properties of sample was checked by measuring upconversion emission and photoacoustic spectra, simultaneously. It is observed that the emission intensity and photoacoustic signal both decreases with time. The maximum photoacoustic signal is obtained around 974 nm wavelength and it indicates its potential for photo-thermal therapy using infrared excitation.


Assuntos
Érbio , Itérbio , Érbio/química , Itérbio/química , Análise Espectral , Tamanho da Partícula , Temperatura
18.
Opt Express ; 30(17): 30135-30148, 2022 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-36242123

RESUMO

We introduce a broadband coherent anti-Stokes Raman scattering (CARS) microscope based on a 2-MHz repetition rate ytterbium laser generating 1035-nm high-energy (≈µJ level) femtosecond pulses. These features of the driving laser allow producing broadband red-shifted Stokes pulses, covering the whole fingerprint region (400-1800 cm-1), employing supercontinuum generation in a bulk crystal. Our system reaches state-of-the-art acquisition speed (<1 ms/pixel) and unprecedented sensitivity of ≈14.1 mmol/L when detecting dimethyl sulfoxide in water. To further improve the performance of the system and to enhance the signal-to-noise ratio of the CARS spectra, we designed a convolutional neural network for spectral denoising, coupled with a post-processing pipeline to distinguish different chemical species of biological tissues.


Assuntos
Aprendizado Profundo , Análise Espectral Raman , Dimetil Sulfóxido , Água , Itérbio
19.
Nanoscale ; 14(39): 14770-14778, 2022 Oct 13.
Artigo em Inglês | MEDLINE | ID: mdl-36178268

RESUMO

Lanthanide-doped fluoride nanocrystals (NCs) are known to exhibit unique optical properties, such as upconversion and downconversion luminescence (UCL and DCL), which can be employed for various applications. In this work, we demonstrate that by doping praseodymium(III) and ytterbium(III) ions (Pr3+ and Yb3+) into a nanosized fluoride matrix (i.e. NaYF4 and LiYF4), it is possible to combine their UCL and DCL properties that can be concurrently used for biomedical applications. In particular, the emissive modes combined in a single nanoparticle co-doped with Pr3+ and Yb3+ include DCL emission (excited at 980 nm and peaked at 1320 nm), which can be used for near infrared (NIR) DCL bioimaging in the NIR-II window of biological tissue transparency (∼1000-1350 nm) and UCL emission (excited at 447 nm and peaked at 275 nm) that can be employed for germicide action (via irradiation by light in the UVC range). A possibility of the latter was demonstrated by the denaturation of double-stranded DNA (dsDNA) into single-stranded ones that was caused by the UVC UCL emission from the NCs under 447 nm irradiation; it was evidenced by the hyperchromicity observed in the irradiated dsDNA solution and also by a fluorometric analysis of DNA unwinding (FADU) assay. Concurrently, the possibility of NIR-II luminescence bioimaging through biological tissues (bovine tooth and chicken flesh) was demonstrated. The proposed concept paves a way for NIR-II imaging guided antimicrobial phototherapy using lanthanide-doped fluoride nanocrystals.


Assuntos
Elementos da Série dos Lantanídeos , Nanopartículas , Animais , Bovinos , DNA , Fluoretos/química , Elementos da Série dos Lantanídeos/química , Luminescência , Nanopartículas/química , Praseodímio , Itérbio/química
20.
J Phys Chem B ; 126(39): 7651-7663, 2022 10 06.
Artigo em Inglês | MEDLINE | ID: mdl-36129784

RESUMO

The influence of ytterbium ions (Yb3+), a commonly used paramagnetic NMR chemical shift reagent, on the physical properties and flip-flop kinetics of dipalmitoylphosphatidylcholine (DPPC) planar supported lipid bilayers (PSLBs) was investigated. Langmuir isotherm studies revealed that Yb3+ interacts strongly with the phosphate headgroup of DPPC, evidenced by the increases in shear and compression moduli. Using sum-frequency vibrational spectroscopy, changes in the acyl chain ordering and phase transition temperature were also observed, consistent with Yb3+ interacting with the phosphate headgroup of DPPC. The changes in the physical properties of the membrane were also observed to be concentration dependent, with more pronounced modification observed at low (50 µM) Yb3+ concentrations compared to 6.5 mM Tb3+, suggesting a cross-linking mechanism between adjacent DPPC lipids. Additionally, the changes in membrane packing and phase transition temperatures in the presence of Tris buffer suggested that a putative Yb(Tris)3+ complex forms that coordinates to the PC headgroup. The kinetics of DPPC flip-flop in the gel and liquid crystalline (lc) phases were substantially inhibited in the presence of Yb3+, regardless of the Yb3+ concentration. Analysis of the flip-flop kinetics under the framework of transition state theory revealed that the free energy barrier to flip-flop in both the gel and lc phases was substantial increased over a pure DPPC membrane. In the gel phase, the trend in the free energy barrier appeared to follow the trend in the shear moduli, suggesting that the Yb3+-DPPC headgroup interaction was driving the increase in the activation free energy barrier. In the lc phase, activation free energies of DPPC flip-flop in the presence of 50 µM or 6.5 mM Yb3+ were found to mirror the free energies of TEMPO-DPPC flip-flop, leading to the conclusion that the strong interaction between Yb3+ and the PC headgroup was essentially manifested as a headgroup charge modification. These studies illustrate that the presence of the lanthanide Yb3+ results in significant modification to the lipid membrane physical properties and, more importantly, results in a pronounced inhibition of native lipid flip-flop.


Assuntos
Elementos da Série dos Lantanídeos , Bicamadas Lipídicas , 1,2-Dipalmitoilfosfatidilcolina/química , Bicamadas Lipídicas/química , Fosfatos , Trometamina , Itérbio
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