Specific Detection of Proteins Using Exceptionally Responsive Magnetic Particles.

Sensitivity and specificity are among the most important parameters for viable sensor technologies based on magnetic nanoparticles. In this work, we describe synthetic routes and analytical approaches to improve both aspects. Magnetic iron oxide particles having diameters of 120, 440, and 700 nm were synthesized, and their surfaces were specifically functionalized. The larger particles showed significantly stronger magnetic signals and responses when compared to commercially available magnetic particles (Dynabeads). A force-based detection method was used to distinguish specifically bound particles (via protein interactions) and nonspecifically bound ones (e.g., via physisorption). In addition, an exchange platform, denoted as exchange-induced remnant magnetization (EXIRM), was developed and utilized to detect label-free proteins specifically. Using EXIRM, the 700 nm magnetic particles showed a 7-fold increase in detection sensitivity when compared to the markedly larger commercially available Dynabeads; furthermore, EXIRM exhibited high specificity, even in a 100-fold increase of nontargeted protein. More generally, particle size effects, reaction times, and dynamic ranges are evaluated and discussed herein.

Magnetic Sensing Potential of Fe3O4 Nanocubes Exceeds That of Fe3O4 Nanospheres.

This paper highlights the relation between the shape of iron oxide (Fe3O4) particles and their magnetic sensing ability. We synthesized Fe3O4 nanocubes and nanospheres having tunable sizes via solvothermal and thermal decomposition synthesis reactions, respectively, to obtain samples in which the volumes and body diagonals/diameters were equivalent. Vibrating sample magnetometry (VSM) data showed that the saturation magnetization (Ms) and coercivity of 100-225 nm cubic magnetic nanoparticles (MNPs) were, respectively, 1.4-3.0 and 1.1-8.4 times those of spherical MNPs on a same-volume and same-body diagonal/diameter basis. The Curie temperature for the cubic Fe3O4 MNPs for each size was also higher than that of the corresponding spherical MNPs; furthermore, the cubic Fe3O4 MNPs were more crystalline than the corresponding spherical MNPs. For applications relying on both higher contact area and enhanced magnetic properties, higher-Ms Fe3O4 nanocubes offer distinct advantages over Fe3O4 nanospheres of the same-volume or same-body diagonal/diameter. We evaluated the sensing potential of our synthesized MNPs using giant magnetoresistive (GMR) sensing and force-induced remnant magnetization spectroscopy (FIRMS). Preliminary data obtained by GMR sensing confirmed that the nanocubes exhibited a distinct sensitivity advantage over the nanospheres. Similarly, FIRMS data showed that when subjected to the same force at the same initial concentration, a greater number of nanocubes remained bound to the sensor surface because of higher surface contact area. Because greater binding and higher Ms translate to stronger signal and better analytical sensitivity, nanocubes are an attractive alternative to nanospheres in sensing applications.

Enzymatic conversion of magnetic nanoparticles to a non-magnetic precipitate: a new approach to magnetic sensing.

Magnetic sensing utilizes the detection of biomolecule-conjugated magnetic nanoparticles (MNPs). Our new strategy offers a novel approach to magnetic sensing where in situ conversion produces a "loss of signal" in the sensing device. This report demonstrates the enzymatic conversion of Fe3O4 MNPs to a non-magnetic precipitate via reduction by l-ascorbic acid generated by the action of alkaline phosphatase.

Enzymatic synthesis of magnetic nanoparticles.

We report the first in vitro enzymatic synthesis of paramagnetic and antiferromagnetic nanoparticles toward magnetic ELISA reporting. With our procedure, alkaline phosphatase catalyzes the dephosphorylation of l-ascorbic-2-phosphate, which then serves as a reducing agent for salts of iron, gadolinium, and holmium, forming magnetic precipitates of Fe45±14Gd5±2O50±15 and Fe42±4Ho6±4O52±5. The nanoparticles were found to be paramagnetic at 300 K and antiferromagnetic under 25 K. Although weakly magnetic at 300 K, the room-temperature magnetization of the nanoparticles found here is considerably greater than that of analogous chemically-synthesized LnxFeyOz (Ln = Gd, Ho) samples reported previously. At 5 K, the nanoparticles showed a significantly higher saturation magnetization of 45 and 30 emu/g for Fe45±14Gd5±2O50±15 and Fe42±4Ho6±4O52±5, respectively. Our approach of enzymatically synthesizing magnetic labels reduces the cost and avoids diffusional mass-transfer limitations associated with pre-synthesized magnetic reporter particles, while retaining the advantages of magnetic sensing.

Fabrication of dense non-circular nanomagnetic device arrays using self-limiting low-energy glow-discharge processing.

We describe a low-energy glow-discharge process using reactive ion etching system that enables non-circular device patterns, such as squares or hexagons, to be formed from a precursor array of uniform circular openings in polymethyl methacrylate, PMMA, defined by electron beam lithography. This technique is of a particular interest for bit-patterned magnetic recording medium fabrication, where close packed square magnetic bits may improve its recording performance. The process and results of generating close packed square patterns by self-limiting low-energy glow-discharge are investigated. Dense magnetic arrays formed by electrochemical deposition of nickel over self-limiting formed molds are demonstrated.

Cubic Silica-Coated and Amine-Functionalized FeCo Nanoparticles with High Saturation Magnetization.

By systematically varying the reaction parameters in a liquid-phase reduction reaction, large FeCo nanocubes with tunable body diagonal lengths of 175, 350, and 450 nm were synthesized. The nanocubes were initially stabilized with poly(vinyl pyrrolidone) (PVP) and then coated with a relatively thin layer of silica (~55 nm thick), which allowed them to retain their cubic shape. The magnetization curves showed that the PVP-stabilized nanocubes exhibited a high saturation magnetization of 167 ± 4 emu/g. The saturation magnetization, however, decreased upon coating with silica to 146 ± 13 emu/g for the particles with 350 and 450 nm FeCo cores and 48 ± 1 emu/g for the particles with 175 nm FeCo cores. The silica-coated FeCo nanocubes were then functionalized with 3-(aminopropyl)-trimethoxysilane (APTMS), and a layer of surface-bound nanoparticle was generated by exposing the resultant amine-functionalized nanocubes to self-assembled monolayers (SAMs) on gold terminated with carboxylic-acid groups.