In situ preparation of high relaxivity iron oxide nanoparticles by coating with chitosan: A potential MRI contrast agent useful for cell tracking

Iron oxide nanocrystals are of considerable interest in nanoscience and nanotechnology because of their nanoscale dimensions, nontoxic nature, and superior magnetic properties. Colloidal solutions of magnetic nanoparticles (ferrofluids) with a high magnetite content are highly desirable for most molecular imaging applications. In this paper, we present a method for in situ coating of superparamagnetic iron oxide (SPIO) with chitosan in order to increase the content of magnetite. Iron chloride salts (Fe³⁺ and Fe²⁺) were directly coprecipitated inside a porous matrix of chitosan by Co-60 γ-ray irradiation in an aqueous solution of acetic acid. Following sonication, iron oxide nanoparticles were formed inside the chitosan matrix at a pH value of 9.5 and a temperature of 50 °C. The [Fe³⁺]:[Fe²⁺]:[NH₄OH] molar ratio was 1.6:1:15.8. The final ferrofluid was formed with a pH adjustment to approximately 2.0/3.0, alongside with the addition of mannitol and lactic acid. We subsequently characterized the particle size, the zeta potential, the iron concentration, the magnetic contrast, and the cellular uptake of our ferrofluid. Results showed a z-average diameter of 87.2 nm, a polydispersity index (PDI) of 0.251, a zeta potential of 47.9 mV, and an iron concentration of 10.4 mg Fe/mL. The MRI parameters included an R1 value of 22.0 mM⁻¹ s⁻¹, an R2 value of 202.6 mM⁻¹ s⁻¹, and a R2/R1 ratio of 9.2. An uptake of the ferrofluid by mouse macrophages was observed. Altogether, our data show that Co-60 γ-ray radiation on solid chitosan may improve chitosan coating of iron oxide nanoparticles and tackle its aqueous solubility at pH 7. Additionally, our methodology allowed to obtain a ferrofluid with a higher content of magnetite and a fairly unimodal distribution of monodisperse clusters. Finally, MRI and cell experiments demonstrated the potential usefulness of this product as a potential MRI contrast agent that might be used for cell tracking.     

Submillimeter ESR spectra of Fe<Superscript>2+</Superscript> ions in synthetic and natural beryl crystals

Electron spin resonance spectra of non-Kramers bivalent iron (Fe²⁺) ions have been detected in synthetic and natural beryl crystals with an iron impurity. The observed ESR spectra have been attributed to resonance transitions of Fe²⁺ ions from the ground (singlet) state to excited (doublet) levels with the splitting Δ = 12.7 cm^–1 between the levels. The experimental angular and frequency dependences of the resonance field of the ESR signal have been described by the spin Hamiltonian with the effective spin S = 1. The analysis of the ESR data and optical absorption spectra indicates that the Fe²⁺ ions are situated in tetrahedral positions and substitute Be²⁺ cations in the beryl structure.     

Suppression of the exaggerated growth of barium ferrite nanoparticles from solution using a partial substitution of Sc<Superscript>3+</Superscript> for Fe<Superscript>3+</Superscript>

The effect of the substitution of Sc³⁺ for Fe³⁺ in barium ferrite on the size of the resulting nanoparticles was studied. These nanoparticles, with the nominal compositions BaFe₁₂O₁₉ and BaFe_11.5Sc_0.5O₁₉, were synthesized hydrothermally at 90–240 °C or by coprecipitation under reflux at 140 °C. The precursors were obtained using (co)precipitation at room temperature. The sizes and morphologies of the precursors and nanoparticles were inspected with transmission electron microscopy, while their structures were confirmed with a combination of X-ray powder and electron diffraction. The samples’ compositions were analyzed with energy-dispersive X-ray spectroscopy. The evolution of the particle size and its distribution with the synthesis temperature and time were studied in pure and Sc-substituted barium ferrite and correlated with the evolution of the magnetic properties. The Sc substitution in the barium ferrite results in the formation of magnetic nanoparticles with applicable magnetic properties and in a significant reduction of the exaggerated particle growth. This was explained on the basis of the reaction kinetics.     

High-Frequency Tunable EPR of Fe<Superscript>2+</Superscript> in the Natural and Synthetic Forsterite

The natural forsterites and their synthetic analogs were investigated on a wide-band EPR spectrometer in the frequency region of 65–850 GHz. Two types of non-Kramers ions Fe²⁺ were discovered at the site M1 (inversion symmetry) and M2 (mirror plane symmetry). The ratio of concentrations of Fe²⁺ in these positions was measured in synthetic and natural crystals. The features of EPR spectra of synthetic and natural forsterite are discussed. Spin Hamiltonian with S = 1 was used for theoretical treatment of angular and field–frequency dependences.     

Magnetic properties of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> surface

The magnetic properties of the magnetite Fe₃O₄(110) surface have been studied by spin resolved Auger electron spectroscopy (SRAES). Experimental spin resolved Auger spectra are presented. The results of calculation of Auger lines polarization carried out on the basis of electronic state density are presented. Problems related to magnetic moments of bivalent (Fe²⁺) and trivalent (Fe³⁺) ions on the Fe₃O₄(110) surface are discussed. It is established that the deposition of a thin bismuth film on the surface results in significant growth of polarization of iron Auger peaks, which is due to additional spin-orbit scattering of electrons by bismuth atoms.     

Synthesis of iron oxide nanoparticles under oxidizing environment and their stabilization in aqueous and non-aqueous media

Synthesis of magnetite (Fe₃O₄) nanoparticles under oxidizing environment by precipitation from aqueous media is not straightforward because Fe²⁺ gets oxidized to Fe³⁺ and thus the ratio of Fe³⁺:Fe²⁺=2:1 is not maintained during the precipitation. A molar ratio of Fe³⁺:Fe²⁺ smaller than 2:1 has been used by many to compensate for the oxidation of Fe²⁺ during the preparation. In this work, we have prepared iron oxide nanoparticles in air environment by the precipitation technique using initial molar ratios Fe³⁺:Fe²⁺?2:1. The phases of the resulting powders have been determined by several techniques. It is found that the particles consist mainly of maghemite with little or no magnetite phase. The particles have been suspended in non-aqueous and aqueous media by coating the particles with a single layer and a bilayer of oleic acid, respectively. The particle sizes, morphology and the magnetic properties of the particles and the ferrofulids prepared from these particles are reported. The average particle sizes obtained from the TEM micrographs are 14, 10 and 9 nm for the water, kerosene and dodecane-based ferrofluids, respectively, indicating a better dispersion in the non-aqueous media. The specific saturation magnetization (σ_s) value of the oleic-acid-coated particles (∼53 emu/g) is found to be lower than that for the uncoated particles (∼63 emu/g). Magnetization σ_s of the dodecane-based ferrofluid is found to be 10.1 emu/g for a volume fraction of particles ?=0.019. Zero coercivity and zero remanance on the magnetization curves indicate that the particles are superparamagnetic (SPM) in nature.     

Coumarin Based Fluorescent Probe for Colorimetric Detection of Fe<Superscript>3+</Superscript> and Fluorescence Turn On-Off Response of Zn<Superscript>2+</Superscript> and Cu<Superscript>2+</Superscript>

A new coumarin based Schiff-base chemosensor-(E)-7-(((8-hydroxyquinolin-2-yl)methylene) amino)-4-methyl-2H-chromen-2-one (H ₁₁ L) was synthesized and evaluated as a colorimetric sensor for Fe³⁺ and fluorescence “turn on-off” response of Zn²⁺ and Cu²⁺ using absorption and fluorescence spectroscopy. Upon treatment with Fe³⁺ and Zn²⁺, the absorption intensity as well as the fluorescence emission intensity increases drastically compared to other common alkali, alkaline earth and transition metal ions, with a distinct color change which provide naked eye detection. Formation of 1:1 metal to ligand complex has been evaluated using Benesi-Hildebrand relation, Job’s plot analyses, ¹H NMR titration as well as ESI-Mass spectral analysis. The complex solution of H ₁₁ L with Zn²⁺ ion exhibited reversibility with EDTA and regenerate free ligand for further Zn²⁺ sensing. H ₁₁ L exhibits two INHIBIT logic gates with two different chemical inputs (i) Zn²⁺ (IN1) and Cu²⁺ (IN2) and (ii) Zn²⁺ (IN1) and EDTA (IN2) and the emission as output. Again, an IMPLICATION logic gate is obtained with Cu²⁺ and EDTA as chemical inputs and emission as output mode. Both free ligand as well as metal-complexes was optimized using density functional theory to interpret spectral properties. The corresponding energy difference between HOMO-LUMO energy gap for H ₁₁ L, H₁₁L-Zn²⁺ and H₁₁L-Cu²⁺ are 2.193, 1.834 and 0.172 eV, respectively.     

Bay Functionalized Perylenediimide with Pyridine Positional Isomers: NIR Absorption and Selective Colorimetric/Fluorescent Sensing of Fe<Superscript>3+</Superscript> and Al<Superscript>3+</Superscript> Ions

Bay functionalized perylene diimide substituted with pyridine isomers, (2-pyridine (2HMP-PDI), 3-pyridine (3-HMP-PDI) and 4-pyridine (4-HMP-PDI)) have been synthesized and explored for selective coloro/fluorimetric sensing of heavy transition metal ions. HMP-PDIs showed strong NIR absorption (760–765 nm) in DMF. The absorption and fluorescence of HMP-PDIs have been tuned by make use of pyridine isomers. Reddish-orange color was observed for 2-HMP-PDI (λ_max = 437, 551, 765 nm) whereas 4-HMP-PDI exhibited light green (λ_max = 432, 522, 765 nm). 3-HMP-PDI showed orange-yellow (λ_max = 431, 524, 762 nm). The fluorescence spectra of 2-, 3- and 4-HMP-PDI showed λ_max at 585, 538, 546 nm, respectively. Interestingly, HMP-PDI dyes showed selective color change (intense pink color) and fluorescence quenching for Fe³⁺ and Al³⁺ metal ions in DMF. Absorbance spectra revealed complete disappearance of NIR absorption and intensification/appearance of new peak at lower wavelength. The concentration dependent studies suggest that 4-HMP-PDI can detect up to 36.52 ppb of Fe³⁺ and 43.12 ppb of Al³⁺ colorimetrically. The interference studies in presence of other metal ions confirmed the good selectivity for Fe³⁺ and Al³⁺. The mechanistic studies indicate that Lewis acidic character of Fe³⁺ and Al³⁺ ions were responsible for selective color change and fluorescence quenching.     

Novel Fluorescent Molecular Clips: Selective Recognition Towards Fe<Superscript>3+</Superscript> in Aqueous Solution

In this paper, we report the synthesis, characterization and Fe³⁺-sensing properties of a series of new artificial fluorescent molecular clips, and structure of clip 1 is confirmed by X-ray crystallography. All these molecular clips had the ability to bind and sense Fe³⁺ selectively through decrease fluorescence responses in THF-MeOH-Water. Fluorimetric titration experiment indicated that the quenching of these compounds’ fluorescence upon Fe³⁺ probably arises from the electron/energy transfer between Fe³⁺ and the excited chemosensors. The limit of detection, linear concentration range and selectivity of the fluorescent molecular clips were evaluated in this study as well.     

Fabrication,structure, and properties of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@C encapsulated with YVO<Subscript>4</Subscript>:Eu<Superscript>3+</Superscript> composites

The use of carbon shells offers many advantages in surface coating or surface modification due to their surface with activated carboxyl and carbonyl groups. In this study, the Fe₃O₄@C@YVO₄:Eu³⁺ composites were prepared through a simple sol–gel process. Reactive carbon interlayer was introduced as a key component, which separates lanthanide-based luminescent component from the magnetite, more importantly, it effectively prevent oxidation of the Fe₃O₄ core during the whole preparation process. The morphology, structure, magnetic, and luminescent properties of the composites were characterized by transmission electron microscopy (TEM), high-resolution TEM, X-ray diffraction, X-ray photoelectron spectra, VSM, and photoluminescent spectrophotometer. As a result, the Fe₃O₄@C/YVO₄:Eu³⁺ composites with well-crystallized and core–shell structure were prepared and the YVO₄:Eu³⁺ luminescent layer decorating the Fe₃O₄@C core–shell microspheres are about 10 nm. In addition, the Fe₃O₄@C@YVO₄:Eu³⁺ composites have the excellent magnetic and luminescent properties, which allow them great potential for bioapplications such as magnetic bioseparation, magnetic resonance imaging, and drug/gene delivery.     

Synthesis of Magnetite Nanoparticles by Precipitation with Forced Mixing

Synthesis of magnetite nanoparticles by precipitation with forced mixing is presented. Using this method it is easy to obtain a high product saturation degree and the constant pH value of the reaction system. The TEM and XRD measurments show that the average size of the product magnetite particles is less than 6.0-nm in the condition of [Fe²⁺]/[Fe³⁺]=0.5. The magnetic properties of the samples are discussed.     

Dual-Functional Fluorescein-Based Chemosensor for Chromogenic Detection of Fe<Superscript>3+</Superscript> and Fluorgenic Detection of HOCl

A novel fluorescein-based dual probe was designed and synthesized. The probe exhibited highly sensitive and selective colormetric response to Fe³⁺ and turn-on fluorescence response towards OCl^? with very low detection limits of 100 and 50 nM, respectively. It was successfully applied for quantitative detection of Fe³⁺ and OCl^? in real water samples. Moreover, probe 1 was expected to be a potentially powerful tool for studying and providing further insights into OCl^? and Fe³⁺ chemistry in the near future.     

Autoionization resonances in the photoabsorption spectra of Fe<Superscript><Emphasis Type="Italic">n</Emphasis>+</Superscript> iron ions

The photoabsorption cross sections of a neutral iron atom, as well as positive Fe⁺ and Fe²⁺ ions, are calculated in the relativistic random-phase approximation with exchange in the energy range 20–160 eV. The wavefunctions of the ground and excited states are calculated in the single-configuration Hartree–Fock–Dirac approximation. The resultant photoabsorption spectra are compared with experimental data and with the results of calculations based on the nonrelativistic spin-polarized version of the random-phase approximation with exchange. Series of autoionization resonance peaks, as well as giant autoionization resonance lines corresponding to discrete transitions 3p → 3d, are clearly observed in the photoabsorption cross sections. The conformity of the positions of calculated peaks of giant autoionization resonances with experimental data is substantially improved by taking into account additionally the correlation electron–electron interaction based on the model of the dynamic polarization potential.     

Nonlinear transmittance of ZnSe:Fe<Superscript>2+</Superscript> crystal at a wavelength of 2.92 μm

ZnSe crystals doped with Fe²⁺ ions are produced with the diffusion method under the conditions for thermodynamic equilibrium of solid ZnSe, solid Fe, and vapors (S_ZnSe-S_Fe-V). The transmittance of the samples is varied from 7 to 50% (in the absence of the antireflection coating) for a wavelength of about 3 μm. It is demonstrated that the transmittance of the ZnSe:Fe²⁺ crystals increases with an increase in the energy density of the high-power laser radiation with a wavelength of 2.92 μm. An equation that describes the propagation of the resonant radiation in a medium with saturable absorption at an arbitrary ratio of the radiation pulse duration to the relaxation time of the medium is introduced for the analysis of the experimental dependence of the transmittance on the energy density.     

Fluorescent carbon dots: facile synthesis at room temperature and its application for Fe<Superscript>2+</Superscript> sensing

A new route for one-pot preparation of carbon dots (CDs) was developed at room temperature using PEG400 as both the carbon source and passitive agent. The new method possesses the advantages of facile, rapid, energy-saving, without any external stimulus and environment friendly. By changing the content of NaOH, the PEG400-CDs with blue-emitting, yellow-emitting, orange red-emitting and red-emitting were obtained, and the formation mechanism were carefully investigated. In addition, a sensitive fluorescence sensor were developed for Fe²⁺ detection based on PEG400-CDs since the fluorescence of PEG400-CDs could be enhanced by Fe²⁺. It was found that there is a good linear relationship between the enhanced fluorescence and Fe²⁺ concentration in the range of 0.5 to 2.0 μmol·L^?1 with the detection limit of 6.0 × 10^?8 mol·L^?1, and Fe²⁺ in water samples was also determined with high accuracy and repeatability.     

Electron paramagnetic resonance study of Fe<Superscript>3+</Superscript> ions at octahedral and tetrahedral mirror symmetry sites in the LiScGeO<Subscript>4</Subscript> crystal

An electron paramagnetic resonance (EPR) study of a synthetic single crystal of LiScGeO₄ doped with Cr ions carried out earlier at the X- and Q-bands at 300, K has indicated additional weak lines. A detailed analysis of these EPR lines, which were tentatively attributed to the Fe³⁺ ions at two different mirror symmetry sites, is presented in this paper. The angular dependences in the three crystallographic planes were resolved by fitting the two distinct spectra denoted Fe³⁺(I) and Fe³⁺(II) with a spin Hamiltonian (S=5/2) of monoclinic symmetry. The rank-4 crystal field tensors at tetrahedral and octahedral sites were calculated with the point-charge model to determine the principal axis orientations of their cubic, tetragonal and trigonal components. A comparative analysis of the zero-field splitting tensors and the crystal field ones indicates that Fe³⁺(I) ions substitute for Sc³⁺ at octahedral sites and Fe³⁺(II) ions substitute for Ge⁴⁺ at tetrahedral sites with no significant distorition of the coordination polyhedra in the structure of LiScGeO₄.     

Synthesis and studies of trisubstituted biphthalonitrile/Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> magnetic hybrid microspheres

New trisubstituted biphthalonitrile/magnetite (TSB/Fe₃O₄) magnetic hybrid microspheres were synthesized from TSB and FeCl₃ · 6H₂O using the method of one-stage thermal temperature crystallization of solvents. The morphology and structure of magnetic hybrid microspheres were inspected using a scanning electron microscope, IR Fourier spectroscopy, and X-ray diffraction. It was found that the grown TSB/Fe₃O₄ magnetic hybrid microspheres represent spherical particles with an average size of ~137 nm and a small size spread. The size and size distribution of magnetic hybrid microspheres can be controlled by a small change in the ratio of TSB and Fe³⁺ ion contents in the microsphere. TSB/Fe₃O₄ hybrid microspheres exhibit a rather high saturation magnetization (58.16 emu g^–1) and new microwave electromagnetic properties, i.e., lower (in comparison with published) dielectric losses at low frequencies; magnetic losses are increased obviously due to an increase in the TSB content. Furthermore, it is detected that magnetic hybrid microspheres absorb microwaves, and strong reflection losses in a wide frequency range are established. The effective reflection loss of–31 dB is obtained in the microwave range from 2 to 16 GHz due to TSB content variations. Wide absorption properties of microwaves along with regular spherical shape and excellent magnetic properties offer wide opportunities for various applications of TSB/Fe₃O₄ magnetic hybrid microspheres as functional materials.     

Re-dispersible Li<Superscript>+</Superscript> and Eu<Superscript>3+</Superscript> co-doped CdS nanoparticles: Luminescence studies

Re-dispersible CdS, 5 at.% Eu³⁺-doped CdS, 2 at.% Li⁺ and 5 at.% Eu³⁺ co-doped CdS nanoparticles in organic solvent are prepared by urea hydrolysis in ethylene glycol medium at a low temperature of 170°C. CdS nanoparticles have spherical shape with a diameter of ∼80 nm. The asymmetric ratio (A ₂₁) of the integrated intensities of the electrical dipole transition to the magnetic dipole transition for 5 at.% Eu³⁺-doped CdS is found to be 3.8 and this ratio is significantly decreased for 2 at.% Li⁺ and 5 at.% Eu³⁺ co-doped CdS (A ₂₁ = 2.6). It establishes that the symmetry environment of Eu³⁺ ion is more favored by Li-doping. Extra peak at 550 nm (green emission) could be seen for 2 and 5 at.% Eu³⁺ co-doped CdS. Also, the significant energy transfer from host CdS to Eu³⁺ is found for 5 at.% Eu³⁺-doped CdS compared to that for 2 at.% Li⁺ and 5 at.% Eu³⁺ co-doped CdS.      

A Novel Naphthalene-Immobilized Nanoporous SBA-15 as a Highly Selective Optical Sensor for Detection of Fe<Superscript>3+</Superscript> in Water

A novel organic-inorganic hybrid optical sensor (SBA-NCO) was designed and synthesized through immobilization of isocyanatopropyl-triethoxysilane and 1-amino-naphthalene onto the surface of SBA-15 by post-grafting method. The characterization of materials using XRD, TEM, N₂ adsorption-desorption, and FT-IR techniques confirmed the successful attachment of organic moieties and preserving original structure of SBA-15 after modification step. Fluorescence experiments demonstrated that SBA-NCO was a highly selective optical sensor for the detection of Fe³⁺ directly in water over a wide range of metal cations including Na⁺, Mg²⁺, Al³⁺, K⁺, Ca²⁺, Cr³⁺, Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Hg²⁺, and Pb²⁺ in a wide pH values.     

Red,Yellow, Blue and Green Emission from Eu<Superscript>3+</Superscript>, Dy<Superscript>3+</Superscript> and Bi<Superscript>3+</Superscript> Doped Y<Subscript>2</Subscript>O<Subscript>3</Subscript>nano-Phosphors

Rare earth elements (RE = Eu³⁺& Dy³⁺)and Bi³⁺ doped Y₂O₃ nanoparticles were synthesized by urea hydrolysis method in ethylene glycol, which acts as reaction medium as well as a capping agent, at a low temperature of 140 °C,followed by calcination of the obtained product. Transmission electron microscope (TEM) images reveals that ovoid shaped Y₂O₃ nanoparticles of around 22–24 nm size range were obtained in this method. The respective RE and Bi³⁺ doped Y₂O₃ precursor nanoparticles when heated at 600 and 750 °C, retains the same shape as that of the as-synthesized Y₂O₃ precursor samples. From EDAX spectra, the incorporation of RE ions into the host has been studied. XRD pattern reveals the crystalline nature of the heated nanoparticles and indicate the absence of any impurity phase other than cubic Y₂O₃.However, the as-synthesized nanoparticles were highly amorphous without the presence of any sharp XRD peaks. Photoluminescence study suggests that the synthesized samples could be used as red (Eu³⁺), yellow (Dy³⁺), blue and green (Bi³⁺)emitting phosphors.