Time-Resolved X-ray Emission Spectroscopy and Synthetic High-Spin Model Complexes Resolve Ambiguities in Excited-State Assignments of Transition-Metal Chromophores: A Case Study of Fe-Amido Complexes.

To fully harness the potential of abundant metal coordination complex photosensitizers, a detailed understanding of the molecular properties that dictate and control the electronic excited-state population dynamics initiated by light absorption is critical. In the absence of detectable luminescence, optical transient absorption (TA) spectroscopy is the most widely employed method for interpreting electron redistribution in such excited states, particularly for those with a charge-transfer character. The assignment of excited-state TA spectral features often relies on spectroelectrochemical measurements, where the transient absorption spectrum generated by a metal-to-ligand charge-transfer (MLCT) electronic excited state, for instance, can be approximated using steady-state spectra generated by electrochemical ligand reduction and metal oxidation and accounting for the loss of absorptions by the electronic ground state. However, the reliability of this approach can be clouded when multiple electronic configurations have similar optical signatures. Using a case study of Fe(II) complexes supported by benzannulated diarylamido ligands, we highlight an example of such an ambiguity and show how time-resolved X-ray emission spectroscopy (XES) measurements can reliably assign excited states from the perspective of the metal, particularly in conjunction with accurate synthetic models of ligand-field electronic excited states, leading to a reinterpretation of the long-lived excited state as a ligand-field metal-centered quintet state. A detailed analysis of the XES data on the long-lived excited state is presented, along with a discussion of the ultrafast dynamics following the photoexcitation of low-spin Fe(II)-Namido complexes using a high-spin ground-state analogue as a spectral model for the 5T2 excited state.

Nanoscale Size Effects on Push-Pull Fe-O Hybridization through the Multiferroic Transition of Perovskite ϵ-Fe2O3.

Multiferroics have tremendous potential to revolutionize logic and memory devices through new functionalities and energy efficiencies. To reach their optimal capabilities will require better understanding and enhancement of the ferroic orders and couplings. Herein, we use ϵ-Fe2O3 as a model system with a simplifying single magnetic ion. Using 15, 20, and 30 nm nanoparticles, we identify that a modified and size-dependent Fe-O hybridization changes the spin-orbit coupling and strengthens it via longer octahedra chains. Fe-O hybridization is modified through the incommensurate phase, with a unique two-step rearrangement of the electronic environment through this transition with attraction and then repulsion of electrons around tetrahedral Fe. Interestingly, size effects disappear in the high-temperature phase where the strongest Fe-O hybridization occurs. By manipulating this hybridization, we tune and control the multiferroic properties.

Simple, Hackable, Size-Selective, Amine-Functionalized Fe-Oxide Nanoparticles for Biomedical Applications.

A facile one-pot method for synthesizing amine-functionalized nonspherical Fe3O4 nanoparticles in gram-scale quantities is presented using just a single source of iron (iron(II) chloride) and an amine (triethylamine). The amine not only transforms iron salt to Fe3O4, but also directs the morphology of the nanoparticles along with the temperature of the reaction and functionalizes them, making the synthesis very economical. By modifying the surface further, these nanoparticles promise to offer useful biomedical applications. For example, after biocide coating, the particles are found to be 100% effective in deactivating methicillin-resistant Staphylococcus aureus (MRSA) bacteria in 2 h. Cellular-uptake studies using biocompatible EDTA-Na3 (N-(trimethoxysilyl-propyl)ethylenediaminetriacetate, trisodium salt)-coated nanoparticles in human glioblastoma U-251 cells show that the majority of the particles are internalized by the cells in the presence of a small dc-magnetic field, making these particles a potential candidate as drug carriers for magnetic field-targeted delivery and hyperthermia.

A Team Approach to Bundle Compliance.

Hospitals are always looking to improve the quality of patient care and avoid hospital-acquired conditions such as ventilator-associated pneumonia (VAP). Currently, there are no set standards regarding interventions to prevent VAP, and there is not a single element that has a direct impact on VAP prevention. By creating an interprofessional team to work together, the quality improvement project was able to evaluate current practice compared with evidence-based practice in the literature to develop a critical care VAP bundle practice, which demonstrated improvement in compliance.

Reverse-Engineering Strain in Nanocrystallites by Tracking Trimerons.

Although strain underpins the behavior of many transition-oxide-based magnetic nanomaterials, it is elusive to quantify. Since the formation of orbital molecules is sensitive to strain, a metal-insulator transition should be a window into nanocrystallite strain. Using three sizes of differently strained Fe3 O4 polycrystalline nanorods, the impact of strain on the Verwey transition and the associated formation and dissolution processes of quasiparticle trimerons is tracked. In 40 and 50 nm long nanorods, increasing isotropic strain results in Verwey transitions going from TV ≈ 60 K to 20 K. By contrast, 700 nm long nanorods with uniaxial strain along the (110) direction have TV ≈ 150 K-the highest value reported thus far. A metal-insulator transition, like TV in Fe3 O4 , can be used to determine the effective strain within nanocrystallites, thus providing new insights into nanoparticle properties and nanomagnetism.

Exploiting shape-selected iron oxide nanoparticles for the destruction of robust bacterial biofilms - active transport of biocides via surface charge and magnetic field control.

Biofilms that form on reusable medical devices are a cause of hospital acquired infections; however, sanitization of biofilms is a challenge due to their dense extracellular matrix. This work presents an innovative strategy using biocide-loaded iron oxide nanoparticles transported within the matrix via a magnetic field to eradicate biofilms. Results show that the active delivery of the biocide to underlying cells effectively penetrates the extracellular matrix and inactivates Methicillin resistant Staphylococcus aureus (MRSA) biofilms (responsible for several difficult-to-treat infections in humans). To optimize this treatment, the loading of spherical, cubic and tetrapod-shaped nanoparticles with a model biocide, CTAB (cetyltrimethylammonium bromide) was studied. Biocide loading was determined to be dependent on the shapes' surface charge density instead of the surface area, meaning that biocide attachment is greater for nanoparticles with sharp edges (e.g. cubes and tetrapods). These results can be used to optimize treatment efficacy, and help further understanding of biofilm and nanoparticle surface zeta potentials, and the nanoparticle-biofilm interactions.

Comparative Heating Efficiency of Cobalt-, Manganese-, and Nickel-Ferrite Nanoparticles for a Hyperthermia Agent in Biomedicines.

In this study, the ac magnetic hyperthermia responses of spinel CoFe2O4, MnFe2O4, and NiFe2O4 nanoparticles of comparable sizes (∼20 nm) were investigated to evaluate their feasibility of use in magnetic hyperthermia. The heating ability of EDT-coated nanoparticles which were dispersed in two different carrier media, deionized water and ethylene glycol, at concentrations of 1 and 2 mg/mL, was evaluated by estimating the specific loss power (SLP) (which is a measure of magnetic energy transformed into heat) under magnetic fields of 15, 25, and 50 kA/m at a constant frequency of 195 kHz. The maximum value of SLP has been found to be ∼315 W/g for CoFe2O4 and ∼295 W/g for MnFe2O4 and NiFe2O4 nanoparticles. We report very promising heating temperature rising characteristics of CoFe2O4, MnFe2O4, and NiFe2O4 nanoparticles under different applied magnetic fields that indicate the effectiveness of these nanoparticles as hyperthermia agents.

A new tool to attack biofilms: driving magnetic iron-oxide nanoparticles to disrupt the matrix.

A main feature of biofilms is the self-produced extracellular polymeric substances (EPSs) that act as a protective shield, preventing biocide penetration. We use magnetic iron oxide nanoparticles (MNPs) in combination with magnetic fields to damage the biofilm matrix and cause detachment. A Methicillin-resistant Staphylococcus aureus (MRSA) biofilm strain is used to demonstrate the efficacy of the methodology with different sizes and concentrations of MNPs under AC and DC applied field conditions. We achieve up to a nearly 5 log10 reduction in biofilm bacteria after treatment with 30 mg mL-1 of 11 nm MNPs using a magnetic field. The MNPs cause significant mechanical disruption to the matrix and lead to biofilm dispersal. In addition, using magnetic hyperthermia further affects biofilm damage.

EDTA-Na3 functionalized Fe3O4 nanoparticles: grafting density control for MRSA eradication.

We report a synthesis strategy to simplify often cumbersome post-synthesis ligand exchange protocols and use that approach to synthesize EDTA-Na3 (N-(trimethoxysilylpropyl)ethylenediaminetriacetate, trisodium salt) functionalized hydrophilic and biocompatible Fe3O4 nanoparticles. The grafting density of EDTA-Na3 has been controlled from 0.07-0.37 µmol m-2 by varying the time at which EDTA-Na3 was added to the reaction. The success of EDTA-Na3 surface functionalization has been verified using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and Mössbauer spectroscopy techniques. Mössbauer spectroscopy results showed the evidence of Fe-EDTA monomer and dimer formation signifying covalent bonding between Fe ions and EDTA-Na3. The earliest addition of EDTA-Na3 resulted in the most stable dispersion of nanoparticles in water and phosphate buffered saline (PBS) which remained stable for more than a month. In addition, our results suggest that these nanoparticles can have useful applications in magnetic hyperthermia and eradication of methicillin-resistant Staphylococcus aureus (MRSA) bacteria in presence of an ac magnetic field.