CO2 switchable nanoparticles: reversible water/organic-phase exchange of gold nanoparticles by gas bubbling
Gold nanoparticles capped with oleylamine can be effectively transferred from an organic solvent to water in the presence of an acetamidine surfactant by CO2 bubbling and then effectively reverted back to the organic phase by N2 bubbling.
A broadening temperature sensitivity range with a core-shell YbEr@YbNd double ratiometric optical nanothermometer.
The chemical architecture of lanthanide doped core–shell up-converting nanoparticles can be engineered to purposely design the properties of luminescent nanomaterials, which are typically inaccessible to their homogeneous counterparts. Such an approach allowed to shift the up-conversion excitation wavelength from ∼980 to the more relevant ∼808 nm or enable Tb or Eu up-conversion emission, which was previously impossible to obtain or inefficient. Here, we address the issue of limited temperature sensitivity range of optical lanthanide based nano-thermometers. By covering Yb–Er co-doped core nanoparticles with the Yb–Nd co-doped shell, we have intentionally combined temperature dependent Er u…
Thin Amphiphilic Polymer-Capped Upconversion Nanoparticles: Enhanced Emission and Thermoresponsive Properties
Upconversion nanoparticles (ß-NaYF4:Er3+, Yb3+, UCNPs) were capped with a thin polymer shell by replacing the oleate ligand of hydrophobic UCNPs by multidentate thiolate-grafting of P(MEO2MA-co-SEMA) copolymers. The presence of the 2-(2-methoxyethoxy)ethyl side chains of MEO2MA extending out of the nanohybrid made them water-dispersible. The UCNP@P(MEO2MA-co-SEMA) nanohybrids exhibited an enhanced emission by up to a factor of 10, as compared with that of their hydrophobic precursor in dichloromethane and even in water (a factor of 2). Moreover, their thermoresponsiveness was modulated by the pH; this is consistent with the presence of some thiol groups at the nanohybrid periphery. Remarkab…
Breaking the Nd3+-sensitized upconversion nanoparticles myth about the need of onion-layered structures
Up to now, most strategies to build efficient 800 nm-light responsive upconversion nanoparticles (UCNPs) have included onion-layered structures, in which Nd3+ is confined within the inorganic crystal structure of at least one layer. We report here an easy room-temperature modular preparation of core-shell UCNPs consisting of NaYF4:Yb,Er(Tm)/NaYF4 (UCCS) with Nd3+ anchored at the organic capping by using cucurbituril[7] (CB[7]) as an adhesive. Strikingly, excitation at 800 nm effectively triggers the upconversion emission of UCCS@CB[7]@Nd nanohybrids.
Upconversion Nanoparticles for Bioimaging and Regenerative Medicine.
Nanomaterials are proving useful for regenerative medicine in combination with stem cell therapy. Nanoparticles can be administrated and targeted to desired tissues or organs and subsequently, be used in non-invasive real-time visualization and tracking of cells by means of different imaging techniques, they can act as therapeutic agent nanocarriers, and can also serve as scaffolds to guide the growth of new tissue. Nanoparticles can be of different chemical nature, such as gold, iron oxide, cadmium selenide, and carbon, and have the potential to be used in regenerative medicine. However, there are still many issues to be solved, such as toxicity, stability, and resident time. Upconversion …
Nanohybrid for Photodynamic Therapy and Fluorescence Imaging Tracking without Therapy
Theranostic upconversion nanoparticles (UCNPs) are ideal candidates for personalized medicine. We present a smart, easy-to-prepare nanohybrid (NH) suitable for NIR-theragnosis and imaging tracking without triggering therapy simultaneously. The photophysical features of each component have been carefully selected in order to maximize the capabilities for theragnosis, in particular, the upconversion emission and the photosensitizer absorption. In addition, NH presents a fluorescent marker with one-photon absorption in the green and two-photon absorption cross-section at NIR wavelengths where the UCNP does not absorb, thus enabling innocuous tracking. Thus, the NH consists of NaYF4:Yb, Er, Tm …
NIR excitation of upconversion nanohybrids containing a surface grafted Bodipy induces oxygen-mediated cancer cell death
We report the preparation of water-dispersible, ca. 30 nm-sized nanohybrids containing NaYF4:Er3+, Yb3+ up-conversion nanoparticles (UCNPs), capped with a polyethylene glycol (PEG) derivative and highly loaded with a singlet oxygen photosensitizer, specifically a diiodo-substituted Bodipy (IBDP). The photosensitizer, bearing a carboxylic group, was anchored to the UCNP surface and, at the same time, embedded in the PEG capping; the combined action of the UCNP surface and PEG facilitated the loading for an effective energy transfer and, additionally, avoided photosensitizer leaching from the nanohybrid (UCNP-IBDP@PEG). The effectiveness of the nanohybrids in generating singlet oxygen after n…
O2(a1Δg) + Mg, Fe, and Ca: experimental kinetics and formulation of a weak collision, multiwell master equation with spin-hopping
The first excited electronic state of molecular oxygen, O(2)(a(1)Δ(g)), is formed in the upper atmosphere by the photolysis of O(3). Its lifetime is over 70 min above 75 km, so that during the day its concentration is about 30 times greater than that of O(3). In order to explore its potential reactivity with atmospheric constituents produced by meteoric ablation, the reactions of Mg, Fe, and Ca with O(2)(a) were studied in a fast flow tube, where the metal atoms were produced either by thermal evaporation (Ca and Mg) or by pulsed laser ablation of a metal target (Fe), and detected by laser induced fluorescence spectroscopy. O(2)(a) was produced by bubbling a flow of Cl(2) through chilled al…
Initial Biological Assessment of Upconversion Nanohybrids
Nanoparticles for medical use should be non-cytotoxic and free of bacterial contamination. Upconversion nanoparticles (UCNPs) coated with cucurbit[7]uril (CB[7]) made by combining UCNPs free of oleic acid, here termed bare UCNPs (UCn), and CB[7], i.e., UC@CB[7] nanohybrids, could be used as photoactive inorganic-organic hybrid scaffolds for biological applications. UCNPs, in general, are not considered to be highly toxic materials, but the release of fluorides and lanthanides upon their dissolution may cause cytotoxicity. To identify potential adverse effects of the nanoparticles, dehydrogenase activity of endothelial cells, exposed to various concentrations of the UCNPs, was determined. Da…
NIR laser scanning microscopy for photophysical characterization of upconversion nanoparticles and nanohybrids
Photophysical characterization of upconversion nanoparticles (UCNPs) and nanohybrids (UCNHs) is more challenging than that of down-conversion nanomaterials. Moreover, it is still difficult to gain knowledge about the homogeneity of the sample and colocalization of emissive chromophores and nanoparticles in nanohybrids. Near infrared laser scanning microscopy (NIR-LSM) is a well-known and useful imaging technique, which enables excitation in the NIR region and has been extensively applied to optical fluorescence imaging of organic fluorophores and nanomaterials, such as quantum dots, which exhibit a short-lived emission. NIR-LSM has recently been used to determine the empirical emission life…
Upconversion nanoparticles with a strong acid-resistant capping
Water-dispersible upconversion nanoparticles (β-NaYF:Yb,Er, UCNP) coated with a thin shell of a biocompatible copolymer comprising 2-hydroxyethylmethacrylate (HEMA) and 2-acrylamido-2-methyl-1-propanesulphonsulphonic acid (AMPS), which we will term COP, have been prepared by multidentate grafting. This capping is remarkably resistant to strong acidic conditions as low as pH 2. The additional functionality of the smart UCNP@COP nanosystem has been proved by its association to a well-known photosensitizer (namely, methylene blue, MB). The green-to-red emission ratio of the UC@COP@MB nanohybrid exhibits excellent linear dependence in the 7 to 2 pH range as a consequence of the release of the d…
The Luminescence of CH3NH3PbBr3Perovskite Nanoparticles Crests the Summit and Their Photostability under Wet Conditions is Enhanced
CH3 NH3 PbBr3 perovskite nanoparticles (PAD ) are prepared with a photoluminescence quantum yield of ≈100% in air atmosphere by using the quasi-spherical shaped 2-adamantylammonium bromide (ADBr) as the only capping ligand. The photostability under wet conditions of this kind of nanoparticles is enhanced by using cucurbit[7]uril-adamantylammonium (AD@CB) host-guest complexes as the capping ligand.
Texture and Phase Recognition Analysis of beta-NaYF4 Nanocrystals
Texture and phase recognition analysis (TPRA) based on electron nanodiffraction technique is used to characterize the geometry of up-conversion nanocrystals (UCNCs) synthesized by the common thermal-decomposition protocol in the presence of a stoichiometric amount of NH4F. Here, we confirmed experimentally that despite the apparently different shapes of samples (hexagons, rods, and cubes), all the nanocrystals are actually beta-phase hexagonal prisms. This is of relevance since many biological features of nanostructures, such as cellular internalization and cytotoxicity, are governed by their geometry. In addition, reproducibility in biological experiments is paramount.
Cucurbit[n]uril-capped upconversion nanoparticles as highly emissive scaffolds for energy acceptors.
Spontaneous adsorption of cucurbit[n]uril CB[n] (n = 6, 7, and 8) on the surface of naked upconversion nanoparticles (UCNPs), in particular, NaYF4:Er3+(2%),Yb3+(18%) gave rise to UCNP@CB[n] exclusion complexes. These complexes proved to be highly stable as well as highly emissive under near-infrared excitation. By using two tricyclic basic dyes (specifically, methylene blue and pyronin Y) as a proof of concept, we demonstrate that the UCNP@CB[n] (n = 6, 7) nanohybrids can form exclusion complexes with this type of dyes via the CB carbonyl free portal, i.e., UCNP@CB@dye hybrids, thus making it possible to locate a high concentration of the dyes close to the UCNP and, consequently, leading to…
Efficient Cementing of CH3NH3PbBr3Nanoparticles to Upconversion Nanoparticles Visualized by Confocal Microscopy
Upconversion-perovskite nanohybrids are prepared by assembling CH3NH3PbBr3 perovskite nanoparticles (PK) with naked NaYF4:Yb3+,Tm3+ nanoparticles (UCn) via an innovative strategy consisting of using cucurbit[7]uril (CB[7]) to anchor the perovskite nanoparticles firmly and closely to the upconversion nanoparticles, thus leading to UCn@PKCB nanohybrids. A commercial multiphoton laser scanning confocal microscope is used to demonstrate the successful assembly. This technique proves to be useful to evaluate luminescence lifetime in the range of several tens of μs and allows visualization of the extraordinarily efficient nontrivial resonance energy transfer from the upconversion nanoparticle to …
Energy transfer in diiodoBodipy-grafted upconversion nanohybrids.
Steady-state and time-resolved emission studies on nanohybrids consisting of NaYF4:Yb,Er and a diiodo-substituted Bodipy (UCNP-IBDP) show that the Yb(3+) metastable state, formed after absorption of a near-infrared (NIR) photon, can decay via two competitive energy transfer processes: sensitization of IBDP after absorption of a second NIR photon and population of Er(3+) excited states.