Search

Periprosthetic joint infection (PJI) is one of the most devastating complications of total joint arthroplasty. The underlying pathogenesis involves the formation of bacterial biofilm that protects the pathogen from the host immune response and antibiotics, making eradication difficult. The aim of this study was to develop a rabbit model of knee PJI that would allow reliable biofilm quantification and permit the study of treatments for PJI. In this work, New Zealand white rabbits (n=19) underwent knee joint arthrotomy, titanium tibial implant insertion, and inoculation with Xen36 (bioluminescent Staphylococcus aureus) or a saline control after capsule closure. Biofilm was quantified via scanning electron microscopy (SEM) of the tibial explant 14 d after inoculation (n=3 noninfected, n=2 infected). Rabbits underwent debridement, antibiotics, and implant retention (DAIR) (n=6) or sham surgery (n=2 noninfected, n=6 infected) 14 d after inoculation, and they were sacrificed 14 d post-treatment. Tibial explant and periprosthetic tissues were examined for infection. Laboratory assays supported bacterial infection in infected animals. No differences in weight or C-reactive protein (CRP) were detected after DAIR compared to sham treatment. Biofilm coverage was significantly decreased with DAIR treatment when compared with sham treatment (61.4 % vs. 90.1 %, p.0011) and was absent in noninfected control explants. In summary, we have developed an experimental rabbit hemiarthroplasty knee PJI model with bacterial infection that reliably produces quantifiable biofilm and provides an opportunity to introduce treatments at 14 d. This model may be used to better understand the pathogenesis of this condition and to measure treatment strategies for PJI.

Monodisperse Fe3O4 nanoparticles (NPs) with excellent water dispersibility and stability were prepared by the introduction of the carboxyl group (−COOH) on the surface of the as-prepared oleyl-capped Fe3O4 NPs. Controlled introduction of the COOH moieties on the NP surface was carried out by a simple ligand exchange reaction using two types of phosphonic acid ligands with dodecyl moiety and the terminal COOH group. The degree of modification of the COOH group on the particle surface was controlled by tuning the molar ratios of the two phosphonic acids. During the ligand exchange reaction, no change was observed in the crystal structure and morphology of the Fe3O4 NPs. The results of Fourier transform infrared (FT-IR) spectroscopy confirmed that the two ligands were bound to the Fe3O4 NP surface through their phosphoric acid functional groups. The surface coverage and molar ratios of the two ligands were evaluated by thermal gravimetric analysis (TGA) and via proton nuclear magnetic resonance (1H NMR) measurements, respectively. Results obtained from the thermal analyses were consistent with the initial molar ratios of the ligands used in the reaction, which reflect on the efficiency of the developed ligand exchange process. Our COOH-modified Fe3O4 NPs could be dispersed in water by deprotonation for over 6 months and exhibit a typical ferrofluid behavior without the addition of other surfactants and dispersants, showing high dispersion stability. Furthermore, the magnetic induction heating performance of the Fe3O4 NPs in aqueous dispersions was evaluated and the specific absorption rate (SAR) value was estimated to be 38.3 W/g Fe. These results suggest that our COOH-modified Fe3O4 NPs with the desired number of COOH surface moieties can be advantageous for applications such as precise surface design, water-based ferrofluid, and hyperthermia treatment.

Spinel ferrite nanocubes (NCs), consisting of pure iron oxide or mixed ferrites, are largely acknowledged for their outstanding performance in magnetic hyperthermia treatment (MHT) or magnetic resonance imaging (MRI) applications while their magnetic particle imaging (MPI) properties, particularly for this peculiar shape different from the conventional spherical nanoparticles (NPs), are relatively less investigated. In this work, we report on a non-hydrolytic synthesis approach to prepare mixed transition metal ferrite NCs. A series of NCs of mixed zinc-cobalt-ferrite were prepared and their magnetic theranostic properties were compared to those of cobalt ferrite or zinc ferrite NCs of similar sizes. For each of the nanomaterials, the synthesis parameters were adjusted to obtain NCs in the size range from 8 up to 15 nm. The chemical and structural nature of the different NCs was correlated to their magnetic properties. In particular, to evaluate magnetic losses, we compared the data obtained from calorimetric measurements to the data measured by dynamic magnetic hysteresis obtained under alternating magnetic field (AMF) excitation. Cobalt-ferrite and zinc-cobalt ferrite NCs showed high specific adsorption rate (SAR) values in aqueous solutions but their heating ability was drastically suppressed once in viscous media even for NCs as small as 12 nm. On the other hand, non-stoichiometric zinc-ferrite NCs showed significant but lower SAR values than the other ferrites, but these zinc-ferrite NCs preserved almost unaltered their heating trend in viscous environments. Also, the presence of zinc in the crystal lattice of zinc–cobalt ferrite NCs showed increased contrast enhancement for MRI with the highest T2 relaxation time and in the MPI signal with the best point spread function and signal-to-noise ratio in comparison to the analogue cobalt-ferrite NC. Among the different compositions investigated, non-stoichiometric zinc-ferrite NCs can be considered the most promising material as a multifunctional theranostic platform for MHT, MPI and MRI regardless of the media viscosity in which they will be applied, while ensuring the best biocompatibility with respect to the cobalt ferrite NCs., Mixed transition metals ferrites nanocubes are here prepared. Their magnetic properties are evaluated to assess their applicability as theranostic tools for magnetic hyperthermia treatment, magnetic resonance imaging and magnetic particles imaging.

Iron oxide nanoparticles (IONPs) have often been investigated for tumor hyperthermia. IONPs act as heating foci in the presence of an alternating magnetic field (AMF). It has been shown that hyperthermia can significantly alter the tumor immune microenvironment. Typically, mild hyperthermia invokes morphological changes within the tumor, which elicits a secretion of inflammatory cytokines and tumor neoantigens. Here, we focused on the direct effect of IONP-induced hyperthermia on the various tumor-resident immune cell subpopulations. We compared direct intratumoral injection to systemic administration of IONPs followed by application of an external AMF. We used the orthotopic 4T1 mouse model, which represents aggressive and metastatic breast cancer with a highly immunosuppressive microenvironment. A non-inflamed and ‘cold’ microenvironment inhibits peripheral effector lymphocytes from effectively trafficking into the tumor. Using intratumoral or systemic injection, IONP-induced hyperthermia achieved a significant reduction of all the immune cell subpopulations in the tumor. However, the systemic delivery approach achieved superior outcomes, resulting in substantial reductions in the populations of both innate and adaptive immune cells. Upon depletion of the existing dysfunctional tumor-resident immune cells, subsequent treatment with clinically approved immune checkpoint inhibitors encouraged the repopulation of the tumor with ‘fresh’ infiltrating innate and adaptive immune cells, resulting in a significant decrease of the tumor cell population., Iron oxide nanoparticles (IONPs) have often been investigated for tumor hyperthermia.

Through diversity of composition, sequence, and interfacial structure, hybrid materials greatly expand the palette of materials available to access novel functionality. The NSF Division of Materials Research recently supported a workshop (October 17–18, 2019) aiming to (1) identify fundamental questions and potential solutions common to multiple disciplines within the hybrid materials community; (2) initiate interfield collaborations between hybrid materials researchers; and (3) raise awareness in the wider community about experimental toolsets, simulation capabilities, and shared facilities that can accelerate this research. This article reports on the outcomes of the workshop as a basis for cross-community discussion. The interdisciplinary challenges and opportunities are presented, and followed with a discussion of current areas of progress in subdisciplines including hybrid synthesis, functional surfaces, and functional interfaces.

Bacterial biofilms associated with orthopedic implants are notorious cell associations of pathogens that show resistance against antibiotic medications and the host immune response. The presence of...

Multifunctional imaging nanoprobes continue to garner strong interest for their great potential in the detection and monitoring of cancer. In this study, we investigate a series of spatially arranged iron oxide nanocube-based clusters (i.e., chain-like dimer/trimer, centrosymmetric clusters, and enzymatically cleavable two-dimensional clusters) as magnetic particle imaging and magnetic resonance imaging probes. Our findings demonstrate that the short nanocube chain assemblies exhibit remarkable magnetic particle imaging signal enhancement with respect to the individually dispersed or the centrosymmetric cluster analogues. This result can be attributed to the beneficial uniaxial magnetic dipolar coupling occurring in the chain-like nanocube assembly. Moreover, we could effectively synthesize enzymatically cleavable two-dimensional nanocube clusters, which upon exposure to a lytic enzyme, exhibit a progressive increase in magnetic particle imaging signal at well-defined incubation time points. The increase in magnetic particle imaging signal can be used to trace the disassembly of the large planar clusters into smaller nanocube chains by enzymatic polymer degradation. These studies demonstrate that chain-like assemblies of iron oxide nanocubes offer the best spatial arrangement to improve magnetic particle imaging signals. In addition, the nanocube clusters synthesized in this study also show remarkable transverse magnetic resonance imaging relaxation signals. These nanoprobes, previously showcased for their outstanding heat performance in magnetic hyperthermia applications, have great potential as dual imaging probes and could be employed to improve the tumor thermo-therapeutic efficacy, while offering a readable magnetic signal for image mapping of material disassemblies at tumor sites.

This paper describes an innovative machine learning (ML) model to predict the performance of different metal oxide photocatalysts on a wide range of contaminants. The molecular structures of metal oxide photocatalysts are encoded with a crystal graph convolution neural network (CGCNN). The structure of organic compounds is encoded via digital molecular fingerprints (MF). The encoded features of the photocatalysts and contaminants are input to an artificial neural network (ANN), named as CGCNN-MF-ANN model. The CGCNN-MF-ANN model has achieved a very good prediction of the photocatalytic degradation rate constants by different photocatalysts over a wide range of organic contaminants. The effects of the data training strategy on the ML model performance are compared. The effects of different factors on photocatalytic degradation performance are further evaluated by feature importance analyses. Examples are illustrated on the use of this novel ML model for optimal photocatalyst selection and for assessing other types of photocatalysts for different environmental applications.

The extremely high sensitivity that has been suggested for magnetic particle imaging has its roots in the unique signal produced by the nanoparticles at the frequencies of the harmonics of the drive field. That sensitivity should be translatable to other methods that utilize magnetic nanoparticle probes, specifically towards magnetic nanoparticle spectroscopy that is used to measure molecular biomarker concentrations for an “in vivo ELISA” assay approach. In this paper, we translate the predicted sensitivity of magnetic particle imaging into a projected sensitivity limit for in vivo ELISA. The simplifying assumptions adopted are: 1) the limiting noise in the detection system is equivalent to the minimum detectable mass of nanoparticles; 2) the nanoparticle’s signal arising from Brownian relaxation is completely eliminated by the molecular binding event, which can be accomplished by binding the nanoparticle to something so massive that it can no longer physically rotate and is large enough that Neel relaxation is minimal. Given these assumptions, the equation for the minimum concentration of molecular biomarker we should be able to detect is obtained and the in vivo sensitivity is estimated to be in the attomolar to zeptomolar range. Spectrometer design and nonspecific binding are the technical limitations that need to be overcome to achieve the theoretical limit presented.

Although iron is one of Earth's most abundant elements, its availability to plants remains an agricultural challenge, particularly in high pH environments. At high pH, iron forms insoluble ferric oxide-hydroxides that makes it inaccessible to plants. It is estimated that 30% of the world's cropland is too alkaline for optimal plant growth. Staple crops, like rice, are particularly susceptible to iron deficiency, thereby, necessitating the need for continued research in developing iron-based fertilizers. Recent studies have demonstrated the potential of using iron oxide nanoparticles (IONPs) as fertilizers to address iron deficiency in plants, but some studies have generated conflicting results. One of the major challenges associated in investigating IONP plant uptake and translocation is the inability to distinguish between intact IONPs versus leached iron ions. In this study, we utilized a new approach based on magnetic particle spectrometry (MPS) to monitor the uptake and distribution of different sized (10 and 20 nm) chelated IONPs in plants. We exposed garden cress (Lepidium sativum) plants to EDTA-capped IONPs and observed an 8-fold enhancement in total biomass and 1.4 times increase in chlorophyll production compared to plants treated with a commercial chelated iron fertilizer (Fe-EDTA). Moreover, we demonstrated that the uptake and tissue distribution of IONPs can be quantitatively monitored using MPS, and the results of the analysis were validated by atomic absorption spectroscopy, which is the conventional method used to study IONP plant uptake. Our study demonstrates that MPS is a reliable, sensitive, and effective analytical tool for the development of IONP-based fertilizers.

For photovoltaic devices based on hybrid organic–inorganic perovskite thin films, the cell architecture is a vital parameter in defining the macroscopic performance. However, the understanding of the correlation between architecture and carrier dynamics in perovskite thin films has remained elusive. In this work, we utilize concerted materials characterization and optical measurements to investigate the role of chloride addition in PSC devices with two different architectures. Perovskite thin films, prepared with varying ratios of methylammonium halide MACl : MAI (0 : 1, 0.5 : 1, 1 : 1, and 2 : 1), were coated on either planar or mesoporous TiO2/FTO substrates. X-ray diffraction analysis reveals that with increasing the ratio of the Cl− precursor, there is an increasing preferential directional growth of the perovskite film in both configurations. Time-resolved photoluminescence spectroscopy was applied to investigate the electron injection dynamics from the photoexcited perovskites to the TiO2. It is found that the interfacial electron injection rate from perovskite to planar TiO2 is accelerated with increasing Cl− content, which explains the increased power conversion efficiencies using Cl−-modified perovskites as photoactive materials. In contrast, Cl− addition demonstrate no discernable influence on electron injection to mesoporous TiO2, suggesting the interfacial charge recombination rather than electron injection give rise to the improved performance observed in the mesoporous configuration. The results presented here, provide a deeper understanding of the mechanism of chloride addition to MAPbI3 solar cells with different architectures.

Nitrogen-doped TiO2 has a great potential as a photocatalyst under visible light irradiation with applications in the removal of air and water pollutants, and the treatment of bacterial contaminations. In this study, nitrogen-doped TiO2 nanoparticles were synthesized via the sol&ndash, gel method and a post-annealing heat treatment approach. The effects of annealing treatment on the photocatalyst crystalline size and degree of crystallinity were analyzed. Methylene blue dye was used as the model water contaminant for the evaluation of the photoactivity of the synthesized nitrogen-doped TiO2 nanoparticles. The degradation of methylene blue was attributed to three mechanisms, i.e., adsorption, photocatalysis, and direct light photolysis. A kinetic model was developed to distinguish the impact of these three different mechanisms on the removal of contaminants. Adsorption and photocatalysis are heterogeneous processes for removing water organic contaminants. The characterization analysis demonstrates that they are relevant to the microstructures and surface chemical compositions of nitrogen-doped TiO2 photocatalysts. The processing&ndash, structure&ndash, performance relationship helped to determine the optimal processing parameters for nitrogen-doped TiO2 photocatalyst to achieve the best performance. While we used methylene blue as the model contaminant, the generalized quantitative model framework developed in this study can be extended to other types of contaminants after proper calibration.

Pediatric implants are a special subclass of a vast number of clinically used medical implants, uniquely designed to address the needs of young patients who are at the onset of their developmental growth stage. Given the vulnerability of the implant receiver, it is crucial that the implants manufactured for small children with birth-associated defects be given careful considerations and great attention to design detail to avoid postoperative complications. In this review, we focus on the most common types of medical implants manufactured for the treatment of birth defects originating from both genetic and environmental causes. Particular emphasis is devoted toward identifying the implant material of choice and manufacturing approaches for the fabrication of pediatric prostheses. Along this line, the emerging role of 3D printing to enable customized implants for infants with congenital disorders is presented, as well as the possible complications associated with prosthetic-related infections that is prevalent in using artificial implants for the treatment of birth malformations.

This study aims to investigate the feasibility of self-healing concrete with fungi. Fusarium oxysporum, a filamentous fungi strain that is capable of producing biomineralization was selected in the study. The growth behaviors of Fusarium oxysporum under the influence of concrete environment were studied under controlled conditions. The metabolism behaviors of Fusarium oxysporum that affect its self-healing capabilities, such as forming spores and growing mycelium were investigated with macroscopic observations as well as microscopic analytic instruments. The results show that Fusarium oxysporum was able to germinate on the surface of concrete and engaged in rapid mycelium development. The alkaline environment has an influence on the growth of fungal mycelium by slowing their growth. However, under favorable conditions, Fusarium oxysporum mycelium covered a surface area of mortar 86 times the area of the original fungi inoculum after 96 h. Such fast growth of Fusarium oxysporum could contribute to high efficiency in healing cracks. Microscopic characterization by SEM and FTIR further confirmed the metabolism activities of fungi produce biominerals inductive to self-healing performance. The fungal mycelium demonstrated hydrophobic nature. Analyses indicated that compared with bacteria-based self-healing, Fusarium oxysporum can potentially significantly increase the healing efficiency. Depending upon the pH value, fungi based healing time is 11.3%, 15.1% and 79.6% of the healing time required with MICP. Besides, the water repellency of mycelium would reduce the water infiltration rate to 17.22% of that of regular concrete surface, a benefit unseen in bacteria induced MICP. Fungi induced self-healing is environmental friendly than MICP process since no toxic gases are released. Overall, this study demonstrated fungi mediated self-healing mechanism via crack filling and improvement of water tightness as a novel strategy to significantly improve the durability concrete.

Magnetic iron oxide nanoparticles (IONPs) are heavily explored as diagnostic and therapeutic agents due to their low cost, tunable properties, and biocompatibility. In particular, upon excitation with an alternating current (AC) magnetic field, the NPs generate localized heat that can be exploited for therapeutic hyperthermia treatment of diseased cells or pathogenic microbes. In this review, we focus on how structural changes and inter-particle interactions affect the heating efficiency of iron oxide-based magnetic NPs. Moreover, we present an overview of the different approaches to evaluate the heating performance of IONPs and introduce a new theranostic modality based on magnetic imaging guided–hyperthermia.

Biofouling is a major problem in water filtration units, which leads to premature system failure. Conventional treatment methods involving the use of chemicals or high-pressure hydraulics exert mechanical strain on filter materials, leading to shortened service lifetimes. In this study, a novel magnetic polymer nanocomposite is fabricated using a blend of high density/ultrahigh molecular weight polyethylene with magnetite nanoparticle (MNP) fillers. The resulting magnetite–polyethylene nanocomposite (MPE-NC) is mechanically robust and can be externally actuated with an alternating magnetic field to generate localized heating that is effective in eradicating bacterial biofilms. The MNPs are functionalized with silane-based coupling agents and crosslinked onto the polyethylene backbone via a reactive extrusion approach, which results in a twofold enhancement in mechanical properties of the polymer matrix. Furthermore, the magnetic hyperthermia performance of the MPE-NC is improved eightfold by replacing undoped magnetite nanospheres with zinc-doped magnetite nanocube fillers, and the magnetic hyperthermia treatment approach is shown to be 12 times more effective in destroying bacterial biofilms compared to a direct heat-treatment method. During hyperthermia treatment, the mechanical integrity of the MPE-NC is preserved, thereby validating the potential of the MPE-NC as a new filter material with high efficiency in biofilm removal and extended durability.

Bacterial biofilms are highly antibiotic resistant microbial cell associations that lead to chronic infections. Unlike free-floating planktonic bacterial cells, the biofilms are encapsulated in a hardly penetrable extracellular polymeric matrix and, thus, demand innovative approaches for treatment. Recent advancements on the development of gel-nanocomposite systems with tailored therapeutic properties provide promising routes to develop novel antimicrobial agents that can be designed to disrupt and completely eradicate preformed biofilms. In our study, we developed a unique thermoresponsive magnetic glycol chitin-based nanocomposite containing d-amino acids and iron oxide nanoparticles, which can be delivered and undergoes transformation from a solution to a gel state at physiological temperature for sustained release of d-amino acids and magnetic field actuated thermal treatment of targeted infection sites. The d-amino acids in the hydrogel nanocomposite have been previously reported to inhibit biofilm formation and also disrupt existing biofilms. In addition, loading the hydrogel nanocomposite with magnetic nanoparticles allows for combination thermal treatment following magnetic field (magnetic hyperthermia) stimulation. Using this novel two-step approach to utilize an externally actuated gel-nanocomposite system for thermal treatment, following initial disruption with d-amino acids, we were able to demonstrate in vitro the total eradication of Staphylococcus aureus biofilms, which were resistant to conventional antibiotics and were not completely eradicated by separate d-amino acid or magnetic hyperthermia treatments.

Iron oxide nanoparticles (IONPs) with high-index facets have shown great potential as high performance T(2) contrast agents for MRI. Previous synthetic approaches focused mainly on ion-directed or oxidative etching methods. Herein, we report a new synthetic route for preparing high-index faceted iron oxide concave nanocubes using a bulky coordinating solvent. Through the systematic replacement of a non-coordinating solvent, 1-octadecene, with trioctylamine, the solvent interaction with the nanoparticle surface is modified, thereby, promoting the growth evolution of the IONPs from spherical to concave cubic morphology. The presence of the bulky trioctylamine solvent results in particle size increase and the formation of nanoparticles with enhanced shape anisotropy. A well-defined concave nanocube structure was evident from the early stages of particle growth, further confirming the important role of bulky coordinating solvents in nanoparticle structural development. The unique concave nanocube morphology has a direct influence on the magnetic properties of the IONPs, ultimately leading to an ultra-high T(2) relaxivity (862.2 mM(−1) s(−1)), and a 2-fold enhancement in T(2)*-weighted in vivo MRI contrast compared to spherical IONP analogs.

We present an interdisciplinary overview of material engineering and emerging applications of iron oxide nanoparticles. We discuss material engineering of nanoparticles in the broadest sense, emphasizing size and shape control, large-area self-assembly, composite/hybrid structures, and surface engineering. This is followed by a discussion of several non-traditional, emerging applications of iron oxide nanoparticles, including nanoparticle lithography, magnetic particle imaging, magnetic guided drug delivery, and positive contrast agents for magnetic resonance imaging. We conclude with a succinct discussion of the pharmacokinetics pathways of iron oxide nanoparticles in the human body –– an important and required practical consideration for any in vivo biomedical application, followed by a brief outlook of the field.

A laboratory experiment in which students synthesize Ag, Au, and Pt nanoparticles (NPs) and use them to modify screen printed carbon electrodes for the electroanalysis of the hydrogen peroxide content in commercially available teeth whitening strips is described. This experiment is designed for two 3-h laboratory periods and can be adapted for upper-division undergraduate students in instrumental analysis, materials science, or physical chemistry laboratories. The experiment presented has already been used as a hands-on component in a Functional Nanomaterials Course, which exposed students to the analysis of the electrochemical properties of metal nanoparticles. Moreover, it allows for teaching the basics of nanoparticle synthesis and enables students to learn the fundamentals of electrochemical sensing with nanostructured materials.

Metastasis accounts for 90% of the mortality associated with breast cancer. Upregulated expression of members of the lysyl oxidase (LOX) family of secreted copper amine oxidases catalyzes the crosslinking of collagens and elastin in the extracellular matrix. LOXs are linked to the development and metastatic progression of breast cancers. Accordingly, aberrant expression of LOX-like 2 (LOXL2) is observed in poorly differentiated, high-grade tumors and is predictive of diseases recurrence, and for decreased overall patient survival. Therefore, LOXL2 expression may serve as a biomarker for breast cancer. Mechanistically, hydrogen peroxide is produced as a byproduct of LOXL2 when using an appropriate substrate, lysine. We exploited this chemistry to generate a revolutionary gold-based electrochemical biosensor capable of accurately detecting nanomolar quantities of LOXL2 in mouse blood, and in human blood samples. Two different sources of the blood samples obtained from breast cancer patients were used in this study indicating the applicability of detecting LOXL2 in breast cancers patients. Limited numbers of urine specimens from breast cancer patients were also tested. Collectively, all of these tests show the promise and potential of this biosensor for detecting LOXL2 as a surrogate biomarker of breast cancer. This work is described in WO 052962 A1 (2014).

A new hydrothermal synthesis approach involving the carbonization of glucose in the presence of wüstite (FeO) nanoparticles is presented, which leads to the fabrication of rapidly acting and potent antibacterial agents based on iron oxide@carbon (IO@C) nanochains. By using nonmagnetic FeO precursor nanoparticles that slowly oxidize into the magnetic Fe3O4 crystal structure under hydrothermal conditions, we were able to prepare well-defined and short-length IO@C nanochains that are highly dispersed in aqueous media and readily interact with bacterial cells, leading to a complete loss in bacterial cell viability within short incubation times at minimal dosage. The smaller IO@C nanochains synthesized using the FeO precursor nanoparticles can reach above 2-fold enhancement in microbe-killing activity when compared to the larger nanochains fabricated directly from Fe3O4 nanoparticles. In addition, the synthesized IO@C nanochains can be easily isolated using an external magnet and be subsequently recycled to effectively eradicate Escherichia coli cells even after five separate treatment cycles.

We examined the effect of TiO2 nanoparticles (NPs) on the growth of maize and soybean plants and associated soil microbial communities. Plants were grown in a greenhouse, and low levels of undoped or nitrogen-doped TiO2 NPs were applied. Plant growth and nutrient content were determined, and effects of NPs on composition of soil microbial communities were examined using terminal restriction fragment length polymorphism analysis (TRFLP) of rDNA. We found no significant effects of TiO2 NPs on plant growth, nutrient content, or the composition of bacterial communities within the rhizosphere. However, arbuscular mycorrhizal fungal communities were affected by application of undoped and nitrogen-doped TiO2 NPs. This observation may be partially attributed to the small but significant TiO2 NP uptake levels in the root tissues of both plants. Our results suggest that even low concentrations of TiO2 NPs may influence some important groups of soil microbes, such as mycorrhizal fungi, but changes in the composition of microbial communities may not affect plant growth under conditions of adequate moisture and nutrients.

Magnetic particle imaging (MPI) is an emerging imaging modality that allows the direct and quantitative mapping of iron oxide nanoparticles. In MPI, the development of tailored iron oxide nanoparticle tracers is paramount to achieving high sensitivity and good spatial resolution. To date, most MPI tracers being developed for potential clinical applications are based on spherical undoped magnetite nanoparticles. For the first time, we report on the systematic investigation of the effects of changes in chemical composition and shape anisotropy on the MPI performance of iron oxide nanoparticle tracers. We observed a 2-fold enhancement in MPI signal through selective doping of magnetite nanoparticles with zinc. Moreover, we demonstrated focused magnetic hyperthermia heating by adapting the field gradient used in MPI. By saturating the iron oxide nanoparticles outside of a field free region (FFR) with an external static field, we can selectively heat a target region in our test sample. By comparing zinc-doped magnetite cubic nanoparticles with undoped spherical nanoparticles, we could show a 5-fold improvement in the specific absorption rate (SAR) in magnetic hyperthermia while providing good MPI signal, thereby demonstrating the potential for high-performance focused hyperthermia therapy through an MPI-guided approach (hMPI).

Perovskite films were prepared using single step solution deposition at different annealing temperatures and annealing times. The crystal structure, phases and grain size were investigated with XRD, XPS and SEM/EDX. The prepared films show a typical orientation of tetragonal perovskite phase and a gradual transition at room temperature from the yellow intermediate phase to the black perovskite phase. Films with high purity were obtained by sintering at 100 °C. In addition, the chemical composition and crystal structure of intermediate phase were investigated in detail. FTIR, UV-vis and NMR spectra revealed the occurance of DMF complexes. Interestingly, the intermediate phase could be transformed to the black perovskite phase upon X-ray irradiation. In addition, the recovery of the aged perovskite films from a yellow intermediate phase back to the black perovskite was shown to be viable via heating and X-ray irradiation.

Dye-sensitized solar cells (DSSCs) based on free-standing, double-walled TiO 2 nanotubes with bamboo-like morphology have been prepared by a sequence of alternating voltage and two-step anodization treatments. The combination of double-walled and bamboo-like morphologies led to an increase in dye loading and an improvement in photoconversion performance. Subsequently, the fabricated dye-sensitized nanotubes used to prepare DSSCs that operate in a frontside illumination mode yielded a significantly high power conversion efficiency of 3.46%, which was approximately two times higher than DSSCs that were fabricated using traditional single-walled TiO 2 nanotube arrays with smooth surfaces. In addition, DSSCs fabricated from nanotubes with higher bamboo ring densities exhibited better conversion efficiencies than those prepared from nanotubes with lower bamboo ring densities. The improved conversion efficiency can be attributed to increased dye loading in the combined double-walled and bamboo-like titania nanostructures.

The affinity of Cd(2+) toward carboxyl-terminated species covalently bound to monodisperse superparamagnetic iron oxide nanoparticles, Fe(3)O(4)(np)-COOH, was investigated in situ in aqueous electrolytes using rotating disk electrode techniques. Strong evidence that the presence of dispersed Fe(3)O(4)(np)-COOH does not affect the diffusion limiting currents was obtained using negatively and positively charged redox active species in buffered aqueous media (pH = 7) devoid of Cd(2+). This finding made it possible to determine the concentration of unbound Cd(2+) in solutions containing dispersed Fe(3)O(4)(np)-COOH, 8 and 17 nm in diameter, directly from the Levich equation. The results obtained yielded Cd(2+) adsorption efficiencies of ~20 μg of Cd/mg of Fe(3)O(4)(np)-COOH, which are among the highest reported in the literature employing ex situ methods. Desorption of Cd(2+) from Fe(3)O(4)(np)-COOH, as monitored by the same forced convection method, could be accomplished by lowering the pH, a process found to be highly reversible.

Nitrogen doped titania nanoparticles were synthesized and deposited as thin films onto glass slides for photodecomposition studies of high molecular weight organics. The decomposition of stearic acid and polyethelyne glycol (PEG) on the nanostructured thin films under visible light irradiation were monitored using FTIR spectroscopy and a decrease in C–H stretch peak area in the 2,700–3,000 cm−1 range was monitored as the organic molecules were photocatalytically destroyed. Conversely, irradiation with visible light only or the whole Xenon lamp spectrum did not result in the degradation of the stearic or PEG coatings on glass in the absence of the nanocatalysts, which demonstrates for the first time visible light photoactivity of nitrogen-doped titania nanoparticle films.

Magnetic particle imaging (MPI) is an emerging imaging modality with promising applications in diagnostic imaging and guided therapy. The image quality in MPI is strongly dependent on the nature of its iron oxide nanoparticle-based tracers. The selection of potential MPI tracers is currently limited, and the underlying physics of tracer response is not yet fully understood. An in-depth understanding of the magnetic relaxation processes that govern MPI tracers, gained through concerted theoretical and experimental work, is crucial to the development of optimized MPI tracers. Although tailored tracers will lead to improvements in image quality, tailored relaxation may also be exploited for biomedical applications or more flexible image contrast, as in the recent demonstration of color MPI.

The growth of cobalt, iron, and platinum and their alloy nanoparticles was investigated with oleic acid and trioctylphosphine oxide as ligands. Both the ligand type and concentration are important in determining the final product of the reactions. With a high concentration of oleic acid, thermal decomposition of dicobalt octacarbonyl and iron pentacarbonyl precursors yields only molecular cluster complex species with oxidized metal centers. However, reduction of platinum acetylacetonate under identical conditions yields nanometer-sized particles. In the presence of a high concentration of trioctylphosphine oxide, only the cobalt system was observed to form a cluster−complex species, while both the iron and platinum systems form nanometer-sized particles. This oxidation process, which forms cluster complexes, provides a digestive ripening mechanism that competes with the Ostwald ripening process, thus affecting the particle size and composition of both the pure metal and alloy nanoparticles.

A nitrogen-doped TiO2 nanocolloid has been successfully prepared and its properties compared with the commercially available TiO2 nanomaterial, Degussa P25. Several characterization techniques, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron spectroscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy, Raman scattering, and UV-visible reflectance spectra, are combined in order to determine the crystal phase and grain size, shape, degree of nitrogen incorporation, and nature of the resultant oxynitride chemical bonding on the surface and in the bulk. The high relative photocatalytic activity of the nitrogen doped-TiO2 nanocolloid is evaluated through a study of the decomposition of methylene blue under visible light excitation. The ease and degree of substitutional-insertional nitrogen doping is held accountable for the significant increase in photocatalytic activity in the porous nanocolloid versus the nitrided commercial nanopowder. It is suggested that the nitrogen incorporation produces an NO bonding region as evidenced by the resulting XPS spectrum.

Two geometrically constrained Cu(I)−monophenanthroline complexes were investigated spectroscopically to study the effects that ligand constraints have on the excited-state dynamics of copper−phenan...

Cu1.8S quantum dots were prepared by using a single-source-precursor type method and investigated in the light of opto-electronic applications. With femtosecond time-resolved transient absorption measurements, the electron relaxation as well as their trapping dynamics could be evaluated. The measurements reveal that the largest and the smallest QD samples prepared exhibit the longest mobility lifetimes, and that the electron-hole relaxation dynamics is strongly dependent on the occurrence of trapping sites. Based on the argument of optical response, it appears that the largest prepared Cu1.8S QDs with band gap energy of 2.35 eV are preferred candidates for opto-electronic device fabrication.

Ordered arrays of TiO2 nanotubes with double-walled structures and bamboo-like morphologies were prepared by a one-step titanium foil anodic oxidation using a solution of NH4F and ethylene glycol as electrolyte. The as-prepared titania nanotubes exhibit double-wall morphology even prior to the heat treatment process. Field emission-scanning electron microscopy (FE-SEM), X-ray powder diffractometry (XRD) and Raman spectroscopy were used to investigate the structure and morphology of the obtained TiO2 nanotubes. The current-versus-time curves were recorded to monitor the anodization process. Structural investigations of the obtained nanotubes revealed the presence of pure anatase phase TiO2 after annealing at 500 °C, as confirmed by XRD and Raman spectroscopy measurements. By optimizing the electrochemical anodization conditions, TiO2 nanotubes with tunable structures can be reproducibly prepared. Keywords: Titania nanotubes, Electrochemical anodization, Bamboo nanostructure, Double-walled nanostructure

Superparamagnetism is a unique feature of magnetic nanoparticles. Spinel ferrite nanoparticles provide great opportunities for studying the mechanism of superparamagnetic properties. CoFe2O4 nanocrystallites have been synthesized with a microemulsion method. The neutron diffraction studies and the temperature-dependent decay of magnetization show the superparamagnetic relaxation occurring in these nanoparticles. The neutron diffraction shows a high degree of inversion with the 78% tetrahedral sites occupied by Fe3+ cations. The nanoparticles with a 12 nm diameter have a blocking temperature around 320 K. The field-cooled and zero-field-cooled magnetization measurements display a divergence below the blocking temperature. The energy barrier distribution of magnetic anisotropy is derived from the temperature-dependent decay of magnetization. The magnetic anisotropy is clearly the origin of the divergence in the field-cooled and zero-field-cooled magnetization measurements. The energy barrier distribution fu...

Size, shape, and compositional control are at the heart of nanochemistry. Herein, we present a novel method that allows control over all three variables in a simple one-step, wet-chemical procedure. One-dimensional (1D) nanomaterials are of great interest for the construction of highperformance thermoelectric (TE) devices. Theoretical calculations indicate that improvement in TE efficiency can be achieved as the diameter of the 1D structures approaches a few nanometers. To date, the most successful synthesis of 1D TE materials has been achieved by electrodeposition within alumina templates. A series of Bi2Te3, [4,5] Bi2 xSbxTe3, [6] Bi2Te3 ySey, [7] and Bi1 xSbx [8, 9] nanowires were prepared by using the template-based method. The advantages of the electrodeposition method include high efficiency, ease of control over composition, highly crystalline products, and room-temperature reaction conditions. However, the diameters of the nanowires synthesized by the template method are well above 10 nm. To get into the sub-10-nm regime, one needs to obtain templates with very narrow channel diameters, which is currently the limiting factor of this technique. However, advances in combining sonochemistry and electrochemistry have provided a new strategy for the synthesis of nanomaterials. The synthesis of quite sophisticated 1D nanomaterials has recently been demonstrated to be possible through careful control of the electrochemistry, sonochemistry, and initial composition of the precursor solutions. As observed, the advantage of the sonoelectrochemical method is that it achieves 1D control without any template, thereby practically overcoming the limitation of generating nanorods with diameters below 10 nm. This diameter is the size regime in which TE properties become enhanced and a controlled synthesis can produce technologically relevant nanomaterials. Herein, we report the first synthesis of monodispersed PbTe nanorods that are sub10 nm in diameter through a sonoelectrochemical technique. Furthermore, we present the effect of changing the concentration of the coordinating ligand on the resulting composition of the synthesized nanomaterials. Changing the metal/ ligand ratio enabled us to tune the composition of the product from pure Te to pure PbTe nanorods. Lead telluride is the material of choice because of its great potential in high-performance TE devices. Furthermore, it allows the mechanisms that lead to control over the resulting nanorod size and composition to be studied. Basically, the synthesis of PbTe nanorods consists of two steps: First, the electrodeposition of PbTe on the surface of the Ti sonication horn, and second, the dispersion of the PbTe nuclei into solution by pulsed sonication. Control over the electrodeposition process is crucial in obtaining pure and highly crystalline PbTe nanoparticles. Interestingly, we found that the Pb/nitrilotriacetic acid (NTA) ratio plays a key role in the synthesis of PbTe nanorods. In contrast to previous studies on the electrodeposition of bulk PbTe, we used a stoichiometric reactant ratio in the synthesis of the nanorods. The introduction of NTA helps to prevent the precipitation of Pb ions as Pb(OH)2. Furthermore, electrochemical studies show that NTA acts as more than a coordinating capping agent: it actually determines the final products of the process. The pH value of the solution was monitored during the electrodeposition, and TeO2 was shown to be sufficiently soluble at pH 7. However, the solubility of NTA was too poor at low pH values to keep the Pb ions coordinated and in solution. Therefore, the solution was kept at approximately pH 8 under our experimental conditions, as TeO2 is dissolved as TeO3 2 ions at this pH value. The overall PbTe reaction equation [Eq. (1)] is (the NTA ligand is omitted for clarity)

Several harmonic spectra are plotted in Figure 2. An important result is the comparison of free particles embedded in agar and films (Figure 2c). The particles embedded in the films are “frozen” in place, while those in agar, unless bound within the matrix, should still have some freedom to rotate. Particles in both should have identical Neel relaxation times, as that is dependent only on the structure of the iron core and not local environment, provided magnetic interactions can be excluded. A calculation of the Neel relaxation time yields values in the range of 0.12-171 microseconds (for crystal anisotropies in the range of 11-21kJ/m3). The Brownian relaxation time for the films is assumed to be infinite, such that relaxation is only possible through the Neel mechanism. However, the Brownian relaxation times for particles in agar are long enough that relaxation is also assumed to be dominated by the Neel mechanism. While Brownian relaxation may play a role in explaining the signal difference, it is likely due to magnetic interactions between neighboring particles that steepen the magnetization curve. Figure 2c demonstrates that a low interparticle distance generally results in a higher signal. In samples with high local concentrations (such as the films presented here, or samples that exhibit significant aggregation), the average distance between two particles is small enough that dipole-dipole interactions must be considered. Such interactions are one possible explanation for the performance of Feridex IV and Resovist.

Films of Co0.85Zn0.15Fe2O4 nanoparticles were prepared on silanized glass substrates using aminobenzoic acid/imidazole-modified magnetic nanoparticles. Dispersive Faraday rotations in the nanoparticulate films were observed as 1.0°–3.0° under relatively low applied magnetic field strengths of less than 500 Oe. The magnitude of the Faraday rotation increases with increasing thickness of the prepared films. No differences in the Faraday rotation were observed for Co0.85Zn0.15Fe2O4 nanoparticles as the particle size varied from 12 to 18 nm.

TiO2 - xNx nanoparticles were prepared by employing the direct amination of 6−10-nm-sized titania particles. Doping on the nanometer scale led to an enhanced nitrogen concentration of up to 8%, compared to ≤2% in thin films and micrometer-scale TiO2 powders. The synthesized TiO2 - xNx nanocrystals are catalytically active and absorb well into the visible region up to 600 nm, thus exemplifying the use of a nanostructure-based synthesis as a means of producing novel photocatalytic materials.

In this feature article, gold nanoparticle conjugates loaded with phthalocyanine-based PDT drugs are prepared and tested for delivery efficiency and PDT efficacy on HeLa cancer cells. It could be shown that the delivery and PDT outcome are strongly affected by the bond that links the drug load to the nanoparticle surface. Whereas labile amino adsorption to the Au nanoparticle surface allows for efficient drug release into the cancer cells and for efficient PDT, a covalent thiol bond to the Au nanoparticle leads to the delivery of the drug into cell vesicles, and no PDT effect is observed. This work highlights the importance of carefully choosing the interaction between drug molecules and the nanoparticle surface.

A highly efficient drug vector for photodynamic therapy (PDT) drug delivery was developed by synthesizing PEGylated gold nanoparticle conjugates, which act as a water-soluble and biocompatible "cage" that allows delivery of a hydrophobic drug to its site of PDT action. The dynamics of drug release in vitro in a two-phase solution system and in vivo in cancer-bearing mice indicates that the process of drug delivery is highly efficient, and passive targeting prefers the tumor site. With the Au NP-Pc 4 conjugates, the drug delivery time required for PDT has been greatly reduced to less than 2 h, compared to 2 days for the free drug.

This study examines the electronic coupling between quantum dots (QDs) and molecules on their surfaces as a function of the modality of their interaction. As a probe, the energy transfer (ET) between CdSe QDs and phthalocyanines (Pcs) was monitored and evaluated with regard to the functionalization of the axial phthalocyanine ligand, bulkiness of the functional group bridging the QD donor and Pc acceptor, and the number of the functionalized axial ligands. New silicon PCs and their conjugates with CdSe QDs were synthesized. The ET efficiency and kinetics were studied by steady state and femtosecond time-resolved absorption spectroscopy. We observed a decrease in ET efficiency with the increase in functional group bulkiness, which could be explained by increasing steric hindrance between the ET pair. In addition, a higher ET efficiency was observed for amino and thiol functionalized Pcs compared to Pcs without functional group on the axial alkyl chain.

Compared with the top-down lithographic techniques, bottom-up chemical synthesis and self-assembly approaches offer much more flexibilities in creating magnetic nanostructures with controlled size, shape, composition and physical properties. This review summarizes some of the latest developments in this field, with emphasis mainly on transition metals, their alloys and metal oxide nanoparticles. The focus is directed towards the conditions of individual particles as well as large assemblies of particles through colloidal chemistry. Furthermore, some of the future directions in nanomagnetism from the perspective of physical chemists is also presented.

The effect of linker chain length on the energy transfer from CdSe quantum dots (QDs) to silicon phthalocyanine (Pc) photodynamic therapy agents was investigated by steady-state and femtosecond time-resolved spectroscopy with 500 nm light for the specific excitation of the QD energy donor. The conjugation between the QD and the Pc was achieved with linker chains varying from 4 to 9 bond lengths by incorporating 1−6 methylene groups into the axial ligand of the Pc. With increasing chain length, the energy-transfer efficiency increased, which appears to be opposed to a purely Forster-type resonance energy-transfer behavior that is commonly discussed for the energy transfer in QD conjugates. The obtained results provide strong evidence for a capping-layer-mediated energy transfer in the QD-based donor−acceptor conjugates.

Investigation of the growth of CdSe nanocrystals ( approximately 160 atoms) to the uniquely stable size of 2 nm allows the monitoring of the crystallization process in semiconductor quantum dots. By using a combination of optical techniques, high-resolution transmission electron microscopy (HRTEM), and powder X-ray diffractometry (XRD), new phenomena were explored during the CdSe nanocrystal growth process, which involved significant morphological reconstruction and crystallization of the initially formed amorphous nanoparticles. During the crystallization, the absorption onset of the CdSe quantum dots blue shifted toward higher energies at 3 eV (414 nm), while the photoluminescence red shifted to lower energies. Furthermore, an apparent increasing Stokes shift was observed during the formation of small CdSe nanoparticles. On the other hand, the photoluminescence excitation spectra showed constant features over the reaction time. Additionally, results from HRTEM and XRD studies show that the CdSe nanoparticles were amorphous at early reaction stages and became better crystallized after longer reaction times, while the particle size remained the same during the crystallization process. These observations demonstrate the important role of the surface on the optical properties of small CdSe quantum dots and facilitated the spectroscopic monitoring of the crystallization process in quantum dots.