Nanosized maghemite (below 10 nm average diameter), surface-functionalized with meso-2,3-dimercaptosuccinic acid (DMSA), was investigated with respect to the content of DMSA molecules attached onto its surface and the onset of S-S bridges due to oxidation of neighboring S-H groups. To support our investigation, we introduced the use of photoacoustic spectroscopy to monitor thiol groups (S-H) conjugated with Raman spectroscopy to monitor the disulfide bridges (S-S). The normalized intensity (N(R)) of the Raman feature peaking at 500 cm(-1) was used to probe the S-S bridge whereas the normalized intensity (N(P)) of the photoacoustic band-S (0.42-0.65 μm) was used to probe the S-H moiety. The perfect linearity observed in the N(R) versus (1 - N(P)) plot strongly supports the oxidation process involving neighboring S-H groups as the DMSA surface grafting coefficient increases whereas the approach used in this report allows the evaluation of the [S-H]/[S-S] ratio. The observation of the reduction of the hydrodynamic diameter as the nominal DMSA-grafting increases supports the proposed model picture, in which the intraparticle (interparticle) S-S bridging takes place at higher (lower) DMSA-grafting values.
Superparamagnetic iron oxide nanoparticles (SPION) are of great interest for application in magnetic fluid hyperthermia (MFH) due to their heat generation capability in an external alternating magnetic field, besides biocompatibility, and surface properties. MFH has emerged as a promisor therapeutic approach for cancer treatment and is based in controlled heating tumor tissue through the accumulation of SPIONs within cancer cells. This work describes a new route for the preparation of folate-conjugated PEGylated SPIONs, which involves the attachment of such molecules at the surface through polycondensation reactions, without the need for coupling agents or prior modification on the species involved. The size of iron oxide cores obtained by transmission electron microscopy was about 12 nm. The conjugation of folate onto SPIONs was confirmed by FTIR spectroscopy. The folate conjugated nanoparticles were colloidal stable in PBS, presenting a hydrodynamic diameter of 109±1 nm and PDI 0.148. The obtained folate-targeted PEGylated SPIONs showed superparamagnetic behavior with a saturation magnetization of 73.1 emu·g −1 at 300 K. Their specific absorption rate (SAR) ranged from 32.8 to 15.0 W g −1 in an alternating magnetic field of 10-16 kA m −1 and frequency of 420-203 kHz. The heat generated was sufficient to raise the sample temperature to the therapeutic range used in MFH establishing this system as promising candidates for use in MFH treatment.
Biocellulose or bacterial cellulose (BC) is a biocompatible (nano) material produced with a three-dimensional network structure composed of microfibrils having nanometric diameters obtained by the Gluconacetobacter xylinus bacteria. BC membranes present relatively high porosity, allowing the incorporation or synthesis in situ of inorganic nanoparticles for multifunctional applications and have been used as flexible membranes for incorporation of magnetic nanocomposite. In this work, highly stable superparamagnetic iron oxide nanoparticles (SPION), functionalized with polyethylene glycol (PEG), with an average diameter of 5 nm and a saturation magnetization of 41 emu/g at 300 K were prepared. PEG-Fe2O3 hybrid was dispersed by mixing a pristine BC membrane in a stable aqueous dispersion of PEG-SPION. The PEG chains at PEG-SPION's surface provide a good permeability and strong affinity between the BC chains and SPION through hydrogen-bonding interactions. PEG-SPION also allow the incorporation of higher content of nanoparticles without compromising the mechanical properties of the nanocomposite. Structural and magnetic properties of the composite have been characterized by XRD, SEM, energy-dispersive X-ray spectroscopy (EDX), magnetization, Raman spectroscopy, and magnetic force microscopy.
We studied the expression pattern of cell adhesion molecules associated to transendothelial migration of leukocytes in different lung's vascular compartments after administration of a magnetic fluid sample containing maghemite nanoparticles surface-coated with meso-2,3-dimercaptosuccinic acid. The analyses were conducted in mice 4 and 12 h after endovenous administration of the magnetic fluid in control mice. Firstly, the migratory activity of leukocytes after magnetic fluid surface-coated with meso-2,3-dimercaptosuccinic acid administration was confirmed using broncho-alveolar lavage and light microscopy. Then, the expression of cell adhesion molecules in the lung's vascular compartments was investigated by immunofluorescence microscopy of frozen sections, using antibodies against L-selectin, P-selectin, E-selectin, macrophage antigen-1, and leukocyte function associated antigen-1. L- and P-selectin showed similar pattern of expression in the pulmonary vasculature in animals treated with magnetic fluid and in the control group. In contrast, macrophage antigen-1 and leukocyte function associated antigen-1 were found in capillary only in animals treated with magnetic fluid surface-coated with meso-2,3-dimercaptosuccinic acid administration. In addition, after magnetic fluid administration E-selectin was found in post-capillary sites. Our findings demonstrated that magnetic fluid surface-coated with meso-2,3-dimercaptosuccinic acid administration exhibits modulation effects on expression patterns of E-selectin, macrophage antigen-1, and leukocyte function associated antigen-1 in the lung's vascular compartments. These findings are very important in a strategy to reduce the potential toxicity of magnetic fluid surface-coated with meso-2,3-dimercaptosuccinic acid administration for medical applications.
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