Silica Shell Thickness Research Articles

A structural, magnetic and colloidal stability study of uncoated and silica coated iron oxide samples prepared in two different surfactants

The discovery of new magnetic materials of interest in the biomedicine field is a relevant topic in current research. For years, our research group has been investigating the obtaining and study of nanostructured magnetic samples that behave superparamagnetically to enable their transport in living organisms. We present here a study that summarizes the structural characteristics, magnetic behavior and stability of two Fe3O4 samples synthesized by coprecipitation that were dispersed using two different surfactants (oleylamine, OL, and oleic acid, OA), and two others prepared from the previous ones by reaction with tetraethyl orthosilicate (TEOS). The relationships between the surfactant used in the synthesis, the presence of a certain maghemite (γ-Fe2O3) content, the influence of silica shell thickness and magnetic behaviour of all samples were systematically studied by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), Mössbauer spectroscopy and H vs. M loops. Rietveld refinements of the XRD profiles confirmed a partial oxidation of the non-silica-coated samples and FTIR spectra of the uncoated samples showed a very strong broad metal-oxygen band and additional sets of bands from the different organic chains of the two surfactants. Individual particles with a mean diameter of 7 and 9 nm were distinguished in TEM images of uncoated magnetic samples. Mössbauer data indicated the presence of non-stoichiometric magnetite in all samples, in agreement with XRD refinements. Magnetic measurements confirmed the superparamagnetic behavior of all the samples. Highest negative zeta potential values are found for the silica covered samples in both acidic and basic medium, being Fe3O4-AO@SiO2 the best suited for the purposes of its dispersibility in future applications. Low polydispersity index (PDI) values confirmed the best stability and dispersibility of all samples investigated in tetrahydrofuran (THF).

Sub-micron colloidosomes with tuneable cargo release prepared using epoxy-functional diblock copolymer nanoparticles

HypothesisPickering emulsions stabilized using epoxy-functional block copolymer nanoparticles should enable the formation of sub-micron colloidosomes that are stable with respect to Ostwald ripening and allow tuneable small-molecule cargo release. ExperimentsEpoxy-functional diblock copolymer nanoparticles of 24 ± 4 nm were prepared via reversible addition-fragmentation chain transfer (RAFT)-mediated dispersion polymerization of methyl methacrylate (MMA) in n-dodecane. Sub-micron water-in-n-dodecane Pickering emulsions were prepared by high-pressure microfluidization. The epoxy groups were then ring-opened using 3-aminopropyltriethoxysilane (APTES) to prepare cross-linked colloidosomes. The colloidosomes survived removal of the aqueous phase using excess solvent. The silica shell thickness could be adjusted from 11 to 23 nm by varying the APTES/GlyMA molar ratio. The long-term stability of the colloidosomes was compared to precursor Pickering emulsions. Finally, the permeability of the colloidosomes was examined by encapsulation and release of a small molecule. FindingsThe Pickering emulsion droplet diameter was reduced from 700 to 200 nm by increasing the salt concentration within the aqueous phase. In the absence of salt, emulsion droplets were unstable due to Ostwald ripening. However, emulsions prepared with 0.5 M NaCl are stable for at least one month. The cross-linked colloidosomes demonstrated much more stable than the precursor sub-micron emulsions prepared without salt. The precursor nanoemulsions exhibited complete release (>99 %) of an encapsulated dye, while higher APTES/GlyMA ratios resulted in much lower dye release, yielding nearly impermeable silica capsules that retained around 95 % of the dye.

The Optimization of the One-Pot Synthesis of Au@SiO2Core-Shell Nanostructures: Modification with Dansyl Group and Their Fluorescent Properties.

This work describes the optimization of the one-pot synthesis of fine core-shell nanostructures based on nanogold (Au NPs) and silica (SiO2). The obtained core-shell nanomaterials were characterized by Transmission Electron Microscopy (TEM and by the method of spectroscopes such as UV-Vis Spectroscopy and Fourier Transform Infrared Spectroscopy (FT-IR). In addition, the measurement of the zeta potential and size of the obtained particles helped present a full characterization of Au@SiO2 nanostructures. The results show that the influence of reagents acting as reducers, stabilizers, or precursors of the silica shell affects the morphology of the obtained material. By controlling the effect of the added silica precursor, the thickness of the shell can be manipulated, the reducer has an effect on the shape and variety, and then the stabilizer affects their agglomeration. This work provides also a new approach for Au@SiO2core-shell nanostructure preparation by further modification with dansyl chloride (DNS-Cl). The results show that, by tuning the silica shell thickness, the intensity of the fluorescence spectrum of Au@SiO2-(CH2)3-NH-DNS nanocomposite is about 12 times higher than that of DNS-Cl.

Preparation and Characterization of Uniform and Controlled Silica Encapsulating on Lithium Yttrium Fluoride-Based Upconversion Nanoparticles.

In this work, we present an advancement in the encapsulation of lithium yttrium fluoride-based (YLiF4:Yb,Er) upconversion nanocrystals (UCNPs) with silica (SiO2) shells through a reverse microemulsion technique, achieving UCNPs@SiO2 core/shell structures. Key parameters of this approach were optimized to eliminate the occurrence of core-free silica particles and ensure a controlled silica shell thickness growth on the UCNPs. The optimal conditions for this method were using 6 mg of UCNPs, 1.5 mL of Igepal CO-520, 0.25 mL of ammonia, and 50 μL of tetraethyl orthosilicate (TEOS), resulting in a uniform silica shell around UCNPs with a thickness of 8 nm. The optical characteristics of the silica-encased UCNPs were examined, confirming the retention of their intrinsic upconversion luminescence (UC). Furthermore, we developed a reliable strategy to avoid the coencapsulation of multiple UCNPs within a single silica shell. This approach led to a tenfold increase in the UC luminescence of the annealed particles compared to their nonannealed counterparts, under identical silica shell thickness and excitation conditions. This significant improvement addresses a critical challenge and amplifies the applicability of the resulting UCNPs@SiO2 core/shell structures in various fields.

Three-dimensionally printable hollow silica nanoparticles for subambient passive cooling

Abstract Solar reflectance and thermal emissivity are critical benchmarks for evaluating the effectiveness of passive cooling strategies. The integration of three-dimensional (3D) printing techniques with passive cooling materials enables local thermal management of multifaceted objects, offering opportunities for unexplored energy-saving applications. For example, conformal printing of cooling materials can mitigate solar absorption caused by the top metal electrodes in solar cells, thereby improving their efficiency and lifetime. In this study, we report the synthesis of 3D printable hollow silica nanoparticles (HSNPs) designed to induce subambient cooling performance under daylight conditions. HSNPs with diameters of 400–700 nm and silica shell thicknesses of approximately 100 nm were synthesized using an in-situ sol–gel emulsion method. Subsequently, these HSNPs were formulated into printable pastes by carefully selecting the mixture concentration and molecular weight of polyvinylpyrrolidone (PVP). The PVP-linked HSNPs exhibited a solar (0.3–2.5 μm) reflectivity of 0.98 and a thermal (8–13 μm) emissivity of 0.93. In contrast to a single silica nanoparticle (NP), the scattering analysis of a single HSNP revealed a distinctive scattering distribution characterized by amplified backward scattering and suppressed forward scattering. In outdoor daytime experiments, the HSNP-printed sample led to the subambient cooling of a dielectric substrate, surpassing the cooling performance of reference materials such as silica NPs, silver pastes, and commercial white plastics and paints.

Accurately Controlled Tumor Temperature with Silica-Coated Gold Nanorods for Optimal Immune Checkpoint Blockade Therapy.

Photothermal therapy (PTT) at mild temperatures ranging from 44 to 45 °C holds tremendous promise as a strategy for inducing potent immunogenic cell death (ICD) within tumor tissues, which can reverse the immunosuppressive tumor microenvironment (ITM) into an immune-responsive milieu. However, accurately and precisely controlling the tumor temperature remains a formidable challenge. Here, we report the precision photothermal immunotherapy by using silica-coated gold nanorods (AuNR@SiO2), and investigating the optimal administration routes and treatment protocols, which enabled to achieve the sustained and controlled mild heating within the tumor tissues. First, the highest photothermal performance of AuNR@SiO2 with 20-nm silica shell thickness than 5 or 40 nm was confirmed invitro and invivo. Then, the optimal conditions for precision immunotherapy were further investigated to produce mild temperature (44 to 45 °C) accurately in tumor tissues. The optimal conditions with AuNR@SiO2 result in a distinct cell death with high early/late apoptosis and low necrosis, leading to very efficient ICD compared to lower or higher temperatures. In colon tumor-bearing mice, intratumorally injected AuNR@SiO2 efficiently promotes a mild temperature within the tumor tissues by local irradiation of near-infrared (NIR) laser. This mild PTT substantially increases the population of mature dendritic cells (DCs) and cytotoxic T cells (CTLs) within tumor tissues, ultimately reversing the ITM into an immune-responsive milieu. Furthermore, we found that the combination mild PTT with AuNR@SiO2 and anti-PD-L1 therapy could lead to the 100% complete regression of primary tumors and immunological memory to prevent tumor recurrence. Collectively, this study demonstrates that AuNR@SiO2 with a robust methodology capable of continuously inducing mild temperature accurately within the ITM holds promise as an approach to achieve the precision photothermal immunotherapy.

Magnetic particle spectroscopy and magnetic particle imaging of zinc and cobalt ferrite nanoparticles: Distinct relaxation mechanisms

Magnetic particle imaging (MPI) is an emerging imaging method based on the nonlinear response of superparamagnetic tracers to a sinusoidal AC magnetic field. Higher harmonics obtained by the Fourier transform of acquired signals form a so-called magnetic particle spectrum, whereby straightforward evaluation of different nanoparticles as potential MPI tracers can be carried out. The shape of the spectra is largely dictated by the combined Néel and Brownian relaxation of superspins, whose relative contributions vary significantly depending on the tracer properties. The present study is focused on the comparison of several Zn ferrite and Co ferrite samples, selected for their different magnetic behaviors, together with the commercial tracer Resovist® (SH U 555 A). A new custom-made magnetic particle spectrometer and a commercial MPI system (Bruker) with comparable AC field amplitudes (∼14 mT) and frequencies (∼25 kHz) are used. Magnetic nanoparticles of Zn and Co ferrites have been synthesized by the thermal decomposition method and by the solvothermal/hydrothermal route, achieving four different samples of magnetic cores with the mean crystallite size in the range of 8–16 nm. From all of them, well-comparable silica-coated particles with a shell thickness of 5–6 nm have been prepared. To analyse the effect of the coating layer and hydrodynamic size, three additional samples have been supplemented: solvothermal Zn ferrite nanoparticles stabilized with a citrate monolayer, the same particles coated with 17 nm thick silica shell, and silica-coated Zn ferrite particles from the thermal decomposition with a higher degree of agglomeration. Fundamental characterizations of the nanomaterials by XRD, XRF, TEM, and DLS are followed by detailed investigations of their magnetic properties and structural peculiarities by SQUID magnetometry and 57Fe Mössbauer spectroscopy. Magnetic particle spectroscopy and subsequent MPI study demonstrate: (i) superior properties of Zn ferrite nanoparticles compared to their Co ferrite counterparts, (ii) only negligible to weak effect of the type/thickness of the coating on signal of Zn ferrite nanoparticles, (iii) comparable performance of the solvothermal Zn ferrite particles with a thin silica shell and of the Resovist® tracer, and importantly, (iv) that suitable choice of the magnetic phase enables to separate the contributions of the Néel and Brownian relaxation on the timescale of MPI.

Sustained activation of persulfate by slow release of Fe(II) from silica-coated nanosized zero-valent iron for in situ chemical oxidation

Sustained activation of persulfate through the slow release of Fe(II) from silica-coated nanosized zero-valent iron (nZVI) particles (nZVI@SiO2) was investigated. Slow release of Fe(II) prevented radical scavenging by excess Fe(II) and increased the radical yield, which improved the stoichiometric efficiency of phenol degradation. Sulfate and hydroxyl radicals were found to be the main oxidative species produced during phenol degradation and were found to make comparable contributions to oxidation. The nZVI@SiO2 particle silica shell thickness controlled the release of Fe(II) and therefore the sustained activation of persulfate and was strongly affected by the synthesis conditions, including the [Si]/[Fe] ratio and silica supply rate. Optimal sustained phenol degradation was achieved when nZVI@SiO2 particles were synthesized using a [Si]/[Fe] ratio of 0.5 and a tetraethyl orthosilicate supply rate of 0.5 mL/min, and this was attributed to the nZVI@SiO2 particles giving an optimal Fe(II) release rate and therefore a high persulfate activation rate and a high phenol removal efficiency. Sustained persulfate activation induced by Fe(II) being slowly released was described well by single-stage first-order kinetics rather than two-stage first-order kinetics typical of unmodified nZVI/persulfate systems. Persulfate was found still to be activated by iron (oxyhydr)oxides minerals after the nZVI@SiO2 particles had been exhausted but the persulfate sustained activation induced by the slow release of Fe(II) played a crucial role in determining the overall degradation efficiency. The results highlight the importance of the slow release of Fe(II) from nZVI-based materials for in situ chemical oxidation through sustained persulfate activation.

Improvement of emission intensity of PbS quantum dots in thick silica shell by initial coating in organic solvent

Abstract Positioning of colloidal quantum dots (QDs) by nanoholes is applicable to fabricating quantum devices such as quantum circuits. A silica coating technique that facilitates the positioning manages the effective size of QDs while preserving the quantum state inside. In the reverse micelle method, which is commonly used for the silica coating, optical properties deteriorate due to the exposure of QD surface to moisture within the reverse micelle. We studied a thin silica coating on the surface of PbS QDs by pyrolyzing tetraethyl orthosilicate in an organic solvent before forming a thick silica shell by the reverse micelle method. As a result, highly luminous silica-coated PbS QDs with a diameter of about 110 nm were realized.

Gold Nanorods with Mesoporous Silica Shell: A Promising Platform for Cisplatin Delivery.

The versatile combination of metal nanoparticles with chemotherapy agents makes designing multifunctional drug delivery systems attractive. In this work, we reported cisplatin's encapsulation and release profile using a mesoporous silica-coated gold nanorods system. Gold nanorods were synthesized by an acidic seed-mediated method in the presence of cetyltrimethylammonium bromide surfactant, and the silica-coated state was obtained by modified Stöber method. The silica shell was modified first with 3-aminopropyltriethoxysilane and then with succinic anhydride to obtain carboxylates groups to improve cisplatin encapsulation. Gold nanorods with an aspect ratio of 3.2 and silica shell thickness of 14.74 nm were obtained, and infrared spectroscopy and ζ potential studies corroborated surface modification with carboxylates groups. On the other hand, cisplatin was encapsulated under optimal conditions with an efficiency of ~58%, and it was released in a controlled manner over 96 h. Furthermore, acidic pH promoted a faster release of 72% cisplatin encapsulated compared to 51% in neutral pH.

Silica-Coated Micrometer-Sized Latex Particles.

A series of silica-coated micrometer-sized poly(methyl methacrylate) latex particles are prepared using a Stöber silica deposition protocol that employs tetraethyl orthosilicate (TEOS) as a soluble silica precursor. Given the relatively low specific surface area of the latex particles, silica deposition is best conducted at relatively high solids to ensure a sufficiently high surface area. Such conditions aid process intensification. Importantly, physical adsorption of chitosan onto the latex particles prior to silica deposition minimizes secondary nucleation and promotes the formation of silica shells: in the absence of chitosan, well-defined silica overlayers cannot be obtained. Thermogravimetry studies indicate that silica formation is complete within a few hours at 20 °C regardless of the presence or absence of chitosan. Kinetic data obtained using this technique suggest that the adsorbed chitosan chains promote surface deposition of silica onto the latex particles but do not catalyze its formation. Systematic variation of the TEOS/latex mass ratio enables the mean silica shell thickness to be tuned from 45 to 144 nm. Scanning electron microscopy (SEM) studies of silica-coated latex particles after calcination at 400 °C confirm the presence of hollow silica particles, which indicates the formation of relatively smooth (albeit brittle) silica shells under optimized conditions. Aqueous electrophoresis and X-ray photoelectron spectroscopy studies are also consistent with latex particles coated in a uniform silica overlayer. The silica deposition formulation reported herein is expected to be a useful generic strategy for the efficient coating of micrometer-sized particles at relatively high solids.

Enhanced Cancer Imaging and Chemo‐Photothermal Combination Therapy by Cancer‐Targeting Bismuth‐Based Nanoparticles

AbstractDue to the complexity and heterogeneity of cancer, the clear and accurate tumor imaging and image‐guided multimodal synergistic therapy are highly in demand. Here, bismuth (Bi)‐based mesoporous‐silica‐coated nanoparticles (BMSNs) are successfully fabricated with the silica shell thickness being lower than the Bi nanoparticle diameter. Then, an MCF‐7 breast cancer‐targeting peptide (termed AR) is modified onto the surface of BMSNs. The obtained nanoparticles (BMSN‐AR) show a significantly higher loading of doxorubicin hydrochloride (DOX). The resultant BMSN‐AR‐DOX can agglomerate in the tumor site, enabling enhanced computed tomography (CT) imaging of the whole tumor. Under 808 nm near‐infrared (NIR) laser irradiation, the BMSN‐AR‐DOX also effectively converts light energy into thermal energy to achieve synergistic chemo‐photothermal therapy in vivo. The chemo‐photothermal combination therapy is found to be more effective than chemotherapy or photothermal therapy alone. This work demonstrates that tumor‐homing peptides can guide nanoparticles to tumors and allow the nanoparticles to enhance cancer imaging and photothermal/chemo combination therapy.

An optical keypad lock with high resettability based on a quantum dot-porphyrin FRET nanodevice.

Due to their appealing properties, nanomaterials have become ideal candidates for the implementation of computing systems. Herein, an optical keypad lock based on a Förster resonance energy transfer (FRET) nanodevice is developed. The nanodevice is composed of a green-emission quantum dot with a thick silica shell (gQD@SiO2) and peripheric blue-emission quantum dots with ultrathin silica spacer (bQD@SiO2), on which 5,10,15,20-tetrakis(4-sulfophenyl)porphyrin (TSPP) is covalently linked. The nanodevice outputs dual emission-based ratiometric fluorescence, depending on the FRET efficiency of bQD-porphyrin pairs, which is highly sensitive to the metalation of TSPP: values are 59.7%, 44.8%, and 10.1% for bQD-Zn(ii)TSPP, bQD-TSPP, and bQD-Fe(iii)TSPP pairs, respectively. As such, by using the competitive chelation-induced transmetalation of TSPP, the nanodevice is capable of implementing a 3-input keypad lock that is unlocked only by the correct input order of Zn(ii) chelator, iron ions, and UV light. Interestingly, the reversible transmetalation of TSPP permits the reset (lock) operation of the keypad lock with the correct input order of ascorbic acid, Zn(ii), and UV light. Application of the nanodevice is exemplified by the construction of paper and cellular keypad locks, respectively, both of which feature signal readability and/or high resettability, showing high potential for personal information identification and bio-encryption applications.

Гибридные сферические микрорезонаторы с люминесцентными органическими красителями FITC и DCM

Luminescent hybrid spherical microresonators of two types consisting of monodisperse spherical silica particles with a diameter of 3.5 mcm coated with either FITC dye molecules or a 200 nm thick mesoporous silica shell containing DCM dye are fabricated. The luminescence spectra of microresonators are studied and the experimental emission spectra are simulated using the method of spherical wave transfer matrices. The ratio of intensities of emission lines into whispering gallery modes with different polarizations and the same polar and radial indices is analyzed. It is shown that the ratio depends on the orientation of the dipole moment of the radiative transition of dye molecules relative to the surface of spherical silica particles.

Hybrid spherical microresonators with luminescent organic dyes FITC and DCM

Luminescent hybrid spherical microresonators of two types consisting of monodisperse spherical silica particles with a diameter of 3.5 μm coated with either FITC dye molecules or a 200 nm thick mesoporous silica shell containing DCM dye are fabricated. The luminescence spectra of microresonators are studied and the experimental emission spectra are simulated using the method of spherical wave transfer matrices. The ratio of intensities of emission lines into whispering gallery modes with different polarizations and the same polar and radial indices is analyzed. It is shown that the ratio depends on the orientation of the dipole moment of the radiative transition of dye molecules relative to the surface of spherical silica particles. Keywords: spherical microresonator, whispering gallery modes, organic dyes, photoluminescence.

Fe3O4-SiO2 Mesoporous Core/Shell Nanoparticles for Magnetic Field-Induced Ibuprofen-Controlled Release.

Hybrid magnetic nanoparticles made up of an iron oxide, Fe3O4, core and a mesoporous SiO2 shell with high magnetization and a large surface area were proposed as an efficient drug delivery platform. The core/shell structure was synthesized by two seed-mediated growth steps combining solvothermal and sol-gel approaches and using organic molecules as a porous scaffolding template. The system presents a mean particle diameter of 30(5) nm (9 nm magnetic core diameter and 10 nm silica shell thickness) with superparamagnetic behavior, saturation magnetization of 32 emu/g, and a significant AC magnetic-field-induced heating response (SAR = 63 W/gFe3O4, measured at an amplitude of 400 Oe and a frequency of 307 kHz). Using ibuprofen as a model drug, the specific surface area (231 m2/g) of the porous structure exhibits a high molecule loading capacity (10 wt %), and controlled drug release efficiency (67%) can be achieved using the external AC magnetic field for short time periods (5 min), showing faster and higher drug desorption compared to that of similar stimulus-responsive iron oxide-based nanocarriers. In addition, it is demonstrated that the magnetic field-induced drug release shows higher efficiency compared to that of the sustained release at fixed temperatures (47 and 53% for 37 and 42 °C, respectively), considering that the maximum temperature reached during the exposure to the magnetic field is well below (31 °C). Therefore, it can be hypothesized that short periods of exposure to the oscillating field induce much greater heating within the nanoparticles than in the external solution.

Characterization and antibacterial activity of silica-coated bismuth (Bi@SiO2) nanoparticles synthesized by pulsed laser ablation in liquid

This study investigates, for the first time, the characteristics and antibacterial activity of elemental bismuth nanoparticles (Bi NPs) synthesized using pulsed laser ablation in liquid (PLAL) coated with silica using the alcohol-ammonia-Tetraethyl orthosilicate (TEOS) method, producing Bi@SiO2 core–shell NPs, and evaluated the effect of Centrifuge selection on the resultant NPs. The synthesized Bi@SiO2 NPs were characterized using Ultraviolet-Visible (UV-Vis) spectroscopy, energy-dispersive X-ray spectroscopy (EDXS), X-ray diffraction spectroscopy (XRD), and transmission electron microscopy (TEM). UV-Vis spectra measurements confirmed the successful coating of NPs and demonstrated that silica coating of Bi NPs increases the stability of the colloidal solution. EDXS and XRD analysis confirmed the preparation of pure metallic Bi NPs coated by SiO2. TEM images showed that Bi NPs were adequately coated and that the thickness of the silica shell increased with the amount of TEOS used. The antibacterial activity of the coated NPs against E. coli and S. aureus was subsequently assessed using the agar diffusion method. Bi@SiO2 NPs exhibited remarkable antibacterial activity, with an increase in efficacy and a higher potency against E. coli compared to uncoated Bi NPs. The diameter of the inhibition zones increased with the silica shell thickness and the NPs’ concentration.

Superparamagnetic and light-emitting bifunctional nanocomposites of iron oxide and erbium or thulium doped yttrium orthovanadate

Advances in biomedical research have increased interest in obtaining and studying new bifunctional materials for use in theragnostic. Here we describe in detail the preparation of new magnetic-fluorescent bifunctional (Y0.9Ln0.1VO4/Fe3O4)@SiO2 and [(Y0.9Ln0.1VO4 @SiO2)/Fe3O4)@SiO2] nanocomposites with Ln = Er or Tm. In addition, their magnetic and optical properties were carefully analyzed. The influence of Fe3O4 content and the silica shell thickness on the fluorescent emission in the VIS-NIR region of Y0.9Ln0.1VO4 cores was evaluated as well as their use as display systems with the possibility of directing them by means of external magnetic fields. Samples were prepared using wet chemistry methods involving low temperatures and short reaction times. Y0.9Ln0.1VO4 samples that are not easily oxidizable were prepared by a hydrothermal method, while Fe3O4 sample was synthesized by a coprecipitation process in which the mixture of precursors was treated at very low temperature to avoid oxidation. The powder amalgamation of both Y0.9Ln0.1VO4 and Fe3O4 samples was possible due to the silica polymeric network synthetized by a modified Stöber method. The purity of all samples was ensured by XRD and FTIR techniques. Diffraction profiles of Y0.9Ln0.1VO4 samples show diffraction maxima that can be indexed to a tetragonal symmetry of space group I41/amd, compatible with the zircon structure-type of YVO4 host. All reflections present in the diffraction profile of Fe3O4 sample can be indexed to a cubic symmetry of space group Fd3̅m, characteristic of an inverse spinel structure-type. The amorphous silica incorporation on the samples was also evaluated by TEM images. Studies of the magnetic behavior and luminescent emission intensity of the investigated samples showed their dependence on both, the silica coating thickness, and the contact or not between the luminescent samples and the magnetic powder.

Silica Shell Thickness-Dependent Fluorescence Properties of SiO2@Ag@SiO2@QDs Nanocomposites.

Silica shell coatings, which constitute important technology for nanoparticle (NP) developments, are utilized in many applications. The silica shell’s thickness greatly affects distance-dependent optical properties, such as metal-enhanced fluorescence (MEF) and fluorescence quenching in plasmonic nanocomposites. However, the precise control of silica-shell thicknesses has been mainly conducted on single metal NPs, and rarely on complex nanocomposites. In this study, silica shell-coated Ag nanoparticle-assembled silica nanoparticles (SiO2@Ag@SiO2), with finely controlled silica shell thicknesses (4 nm to 38 nm), were prepared, and quantum dots (QDs) were introduced onto SiO2@Ag@SiO2. The dominant effect between plasmonic quenching and MEF was defined depending on the thickness of the silica shell between Ag and QDs. When the distance between Ag NPs to QDs was less than ~10 nm, SiO2@Ag@SiO2@QDs showed weaker fluorescence intensities than SiO2@QD (without metal) due to the quenching effect. On the other hand, when the distance between Ag NPs to QDs was from 10 nm to 14 nm, the fluorescence intensity of SiO2@Ag@SiO2@QD was stronger than SiO2@QDs due to MEF. The results provide background knowledge for controlling the thickness of silica shells in metal-containing nanocomposites and facilitate the development of potential applications utilizing the optimal plasmonic phenomenon.

A FRET sensor based on quantum dots-porphyrin assembly for Fe(III) detection with ultra-sensitivity and accuracy.

Exploring sensors based on Förster resonance energy transfer (FRET) systems enables the continuous development of biological sensing technologies. Herein, we report the construction of a FRET sensor with dual-emissive quantum dots (QDs) and meso-tetra(4-sulfonatophenyl) porphine (TSPP). The sensor is composed of mesial green-emissive QDs with a thick silica shell (gQD@SiO2) and circumjacent blue-emissive QDs coated with ultra-thin silica spacer, on which is linked TSPP (bQD@SiO2-TSPP). The gQD@SiO2 endows the sensor with a fluorescent background. Due to the ultra-thin silica spacing, coupled with the superior resonance effect of bQD fluorescence and the Soret-band absorption of TSPP, the FRET efficiency is highly sensitive to the chelation state of TSPP. Relying on the absorbance transition of TSPP complexed with Fe(III), the FRET sensor is applied for ultra-sensitive Fe(III) detection. In aqueous solution, the sensor is demonstrated to linearly detect Fe(III) in the range of 0-1μM, with a limit of detection (LOD) of 40nM. More importantly, reliable Fe(III) detection can be achieved via the specific complexation of Fe(III) by TSPP and the ratiometric fluorescent response. As such, the inter-/intra-day precisions in standard samples, as well as the recovery rate in biological matrices, are fully validated. The excellent analytical performance, in combination with the excellent biocompatibility of the FRET sensor, allows semi-quantitative Fe(III) imaging in living cells.