Computational and experimental approach to understanding the structural interplay of self-assembled end-terminated alkanethiolates on gold surfaces.

Applications of self-assembled monolayers (SAMs) on surfaces are prevalent in modern technologies and drives the need for a better understanding of the surface domain architecture of SAMs. To explore structural interaction at the interface between gold surfaces and a hydroxyl-terminated alkanethiol, 11-hydroxy-1-undecanethiol, (C11TH) we have employed a combined computational and experimental approach. Density functional theory (DFT) calculations were carried out on the thiol-gold interface using both the Perdew-Burke-Ernzerhof (PBE) and van der Waals (optB86b) density functionals. Our ab initio molecular dynamics (AIMD) simulations revealed that the interface consists of four different distinguished phases, each with different C11TH orientations. Experiments involved deposition of C11TH SAMs onto gold, with the resultant surfaces examined with X-ray photoelectron spectroscopy (XPS) and ellipsometry. Weighted average projected density of states (PDOS) of the different phases were photoionization cross section corrected and these were confirmed by experimental XPS data. Computed molecular parameters including tilt angles and the thickness of SAMs also agreed with the XPS and ellipsometry results. Hydrogen bonding arising from the terminal hydroxyl groups is the primary factor governing the stability of the four phases. Experimental results from XPS and ellipsometry along with DFT simulation results provide insights into the formation of the different orientations of SAM on Au(111) which will guide future efforts in the self-assembled SAMs architecture for other thiols or metal substrates.

Fabricated nanogap-rich plasmonic nanostructures through an optothermal surface bubble in a droplet.

A rapid and cost-effective method for the fabrication of nanogap-rich structures is demonstrated in this Letter. The method utilizes the Marangoni convection around an optothermal surface bubble inside a liquid droplet with a nanoliter volume. The liquid droplet containing metallic nanoparticles reduces the sample consumption and confines the liquid flow. The optothermal surface bubble creates a strong convective flow that allows for the rapid deposition of the metallic nanoparticles to form nanogap-rich structures on any substrate under ambient conditions. This method will enable a broad range of applications such as biosensing, environmental analysis, and nonlinear optics.

Experimental and Numerical Investigation of the Silicon Particle Distribution in Electrospun Nanofibers.

The properties of ceramic materials are dependent on crystal sizes and their distribution. These parameters can be controlled using electrospinning of the two-phase mixed system. The preceramic solution consists of silicon nanoparticles and polyacrylonitrile (PAN) polymer mixture. Particle distribution during the electrospinning technique was characterized using transmission electron microscopy and modeled using the finite element method. The experimental and numerical results were in agreement. Large silicon particles were located in the skin and the smaller ones were located at the core. This was illustrated by the migration rate from the core, which was the fastest for large particles and diminished as the particles become smaller in size. The threshold for Stokes number was found to be around 2.2 × 10-4 with a critical particle size of 1.0 × 10-7 m in diameter. The current results are very promising, as it demonstrated a novel way for the fabrication of PAN/Si ceramic nanofibers with a gradient of particle size and properties from the skin to the core.

Bioluminescent magnetic nanoparticles as potential imaging agents for mammalian spermatozoa.

BACKGROUND: Nanoparticles have emerged as key materials for developing applications in nanomedicine, nanobiotechnology, bioimaging and theranostics. Existing bioimaging technologies include bioluminescent resonance energy transfer-conjugated quantum dots (BRET-QDs). Despite the current use of BRET-QDs for bioimaging, there are strong concerns about QD nanocomposites containing cadmium which exhibits potential cellular toxicity. RESULTS: In this study, bioluminescent composites comprised of magnetic nanoparticles and firefly luciferase (Photinus pyralis) are examined as potential light-emitting agents for imaging, detection, and tracking mammalian spermatozoa. Characterization was carried out using infrared spectroscopy, TEM and cryo-TEM imaging, and ζ-potential measurements to demonstrate the successful preparation of these nanocomposites. Binding interactions between the synthesized nanoparticles and spermatozoon were characterized using confocal and atomic/magnetic force microscopy. Bioluminescence imaging and UV-visible-NIR microscopy results showed light emission from sperm samples incubated with the firefly luciferase-modified nanoparticles. Therefore, these newly synthesized luciferase-modified magnetic nanoparticles show promise as substitutes for QD labeling, and can potentially also be used for in vivo manipulation and tracking, as well as MRI techniques. CONCLUSIONS: These preliminary data indicate that luciferase-magnetic nanoparticle composites can potentially be used for spermatozoa detection and imaging. Their magnetic properties add additional functionality to allow for manipulation, sorting, or tracking of cells using magnetic techniques.

Janus magnetic nanoparticles with a bicompartmental polymer brush prepared using electrostatic adsorption to facilitate toposelective surface-initiated ATRP.

Utilizing the inherent negative charge of mica surfaces, amine-functionalized magnetic nanoparticles (Fe3O4/NH2) were electrostatically adsorbed onto the mica such that surface-initiated ATRP could be used to grow poly(n-isopropylacrylamide) (PNIPAM) from the exposed hemisphere. By reducing the solution pH, a positive charge generated on the mica was used to release the nanoparticles from the substrate. A second ATRP reaction was carried out to grow poly(methacrylic acid) (PMAA) from the initiated surfaces. As a result, the Fe3O4/NH2 core has a polymer shell with one hemisphere PMAA and the other hemisphere PNIPAM-b-PMAA resulting in the PMAA-Fe3O4-PNIPAM-b-PMAA bicompartmental polymer Janus nanoparticles. Elemental and functional group compositions were confirmed using ATR-FTIR, XPS, and EDS. Imaging with AFM, SEM, and TEM showed the evolution of the Janus nanoparticle morphology. This study demonstrates a facile and innovative scheme involving a noncovalent solid protection technique combined with sequential, surface-confined controlled radical polymerizations for the production of multicomponent nanocomposites.

Adsorptive properties and on-demand magnetic response of lignin@Fe3O4 nanoparticles at castor oil-water interfaces.

Lignin@Fe3O4 nanoparticles adsorb at oil-water interfaces, form Pickering emulsions, induce on-demand magnetic responses to break emulsions, and can sequester oil from water. Lignin@Fe3O4 nanoparticles were prepared using a pH-induced precipitation method and were fully characterized. These were used to prepare Pickering emulsions with castor oil/Sudan red G dye and water at various oil/water volume ratios and nanoparticle concentrations. The stability and demulsification of the emulsions under different magnetic fields generated with permanent magnets (0-540 mT) were investigated using microscopy images and by visual inspection over time. The results showed that the Pickering emulsions were more stable at the castor oil/water ratio of 50/50 and above. Increasing the concentration of lignin@Fe3O4 improved the emulsion stability and demulsification rates with 540 mT applied magnetic field strength. The adsorption of lignin@Fe3O4 nanoparticles at the oil/water interface using 1-pentanol evaporation through Marangoni effects was demonstrated, and magnetic manipulation of a lignin@Fe3O4 stabilized castor oil spill in water was shown. Nanoparticle concentration and applied magnetic field strengths were analyzed for the recovery of spilled oil from water; it was observed that increasing the magnetic strength increased oil spill motion for a lignin@Fe3O4 concentration of up to 0.8 mg mL-1 at 540 mT. Overall, this study demonstrates the potential of lignin-magnetite nanocomposites for rapid on-demand magnetic responses to externally induced stimuli.

Fabrication and Characterization of Electrospun Poly(acrylonitrile-co-Methyl Acrylate)/Lignin Nanofibers: Effects of Lignin Type and Total Polymer Concentration.

Lignin macromolecules are potential precursor materials for producing electrospun nanofibers for composite applications. However, little is known about the effect of lignin type and blend ratios with synthetic polymers. This study analyzed blends of poly(acrylonitrile-co-methyl acrylate) (PAN-MA) with two types of commercially available lignin, low sulfonate (LSL) and alkali, kraft lignin (AL), in DMF solvent. The electrospinning and polymer blend solution conditions were optimized to produce thermally stable, smooth lignin-based nanofibers with total polymer content of up to 20 wt % in solution and a 50/50 blend weight ratio. Microscopy studies revealed that AL blends possess good solubility, miscibility, and dispersibility compared to LSL blends. Despite the lignin content or type, rheological studies demonstrated that PAN-MA concentration in solution dictated the blend's viscosity. Smooth electrospun nanofibers were fabricated using AL depending upon the total polymer content and blend ratio. AL's addition to PAN-MA did not affect the glass transition or degradation temperatures of the nanofibers compared to neat PAN-MA. We confirmed the presence of each lignin type within PAN-MA nanofibers through infrared spectroscopy. PAN-MA/AL nanofibers possessed similar morphological and thermal properties as PAN-MA; thus, these lignin-based nanofibers can replace PAN in future applications, including production of carbon fibers and supercapacitors.

Facile fabrication and characterization of kraft lignin@Fe3O4 nanocomposites using pH driven precipitation: Effects on increasing lignin content.

This work offers a facile fabrication method for lignin nanocomposites through the assembly of kraft lignin onto magnetic nanoparticles (Fe3O4) based on pH-driven precipitation, without needing organic solvents or lignin functionalization. Kraft lignin@Fe3O4 multicore nanocomposites fabrication proceeded using a simple, pH-driven precipitation technique. An alkaline solution for kraft lignin (pH 12) was rapidly injected into an aqueous-based Fe3O4 nanoparticle colloidal suspension (pH 7) under constant mixing conditions, allowing the fabrication of lignin magnetic nanocomposites. The effects of increasing lignin to initial Fe3O4 mass content (g/g), increasing in ratio from 1:1 to 20:1, are discussed with a complete chemical, structural, and morphological characterization. Results showed that nanocomposites fabricated above 5:1 lignin:Fe3O4 had the highest lignin coverage and content (>20%), possessed superparamagnetic properties (Ms ≈ 45,000 A·m2/kg2); had a negative surface charge (-30 mV), and formed multicore nanostructures (DH ≈ 150 nm). The multicore lignin@Fe3O4 nanocomposites allowed rapid magnetically induced separations from suspension. After 5 min exposure to a rare-earth neodymium magnet (1.27 mm × 1.27 mm × 5.08 mm), lignin@Fe3O4 nanocomposites exhibited a maximum methylene blue removal efficiency of 74.1% ± 7.1%. These nanocomposites have potential in magnetically induced separations to remove organic dyes, heavy metals, or other lignin adsorbates.

Optothermal microbubble assisted manufacturing of nanogap-rich structures for active chemical sensing.

Guiding analytes to the sensing area is an indispensable step in a sensing system. Most of the sensing systems apply a passive sensing method, which waits for the analytes to diffuse towards the sensor. However, passive sensing methods limit the detection of analytes to a picomolar range on micro/nanosensors for a practical time scale. Therefore, active sensing methods need to be used to improve the detection limit in which the analytes are forced to concentrate on the sensors. In this article, we have demonstrated the manufacturing of nanogap-rich structures for active chemical sensing. Nanogap-rich structures are manufactured from metallic nanoparticles through an optothermally generated microbubble (OGMB) which is a laser-induced micron-sized bubble. The OGMB induces a strong convective flow that helps to deposit metallic nanoparticles to form nanogap-rich structures on a solid surface. In addition, the OGMB is used to guide and concentrate analytes towards the nanogap-rich structures for the active sensing of analytes. An active sensing method can improve the detection limit of chemical substances by an order of magnitude compared to a passive sensing method. The microbubble assisted manufacturing of nanogap-rich structures together with an active analyte sensing method paves a new way for advanced chemical and bio-sensing applications.

Optimization and Structural Stability of Gold Nanoparticle-Antibody Bioconjugates.

Gold nanoparticles (AuNPs) bound with biomolecules have emerged as suitable biosensors exploiting unique surface chemistries and optical properties. Many efforts have focused on antibody bioconjugation to AuNPs resulting in a sensitive bioconjugate to detect specific types of bacteria. Unfortunately, bacteria thrive under various harsh environments, and an understanding of bioconjugate stability is needed. Here, we show a method for optimizing Listeria monocytogenes polyclonal antibodies bioconjugation mechanisms to AuNPs via covalent binding at different pH values, from 2 to 11, and 2-(N-morpholino)ethanesulfonic acid (MES), 3-(N-morpholino)propanesulfonic acid, NaOH, HCl conditions. By fitting Lorentz curves to the amide I and II regions, we analyze the stability of the antibody secondary structure. This shows an increase in the apparent breakdown of the antibody secondary structure during bioconjugation as pH decreases from 7.9 to 2. We find variable adsorption efficiency, measured as the percentage of antibody adsorbed to the AuNP surface, from 17 to 27% as pH increases from 2 to 6 before decreasing to 8 and 13% at pH 7.9 and 11, respectively. Transmission electron microscopy (TEM) analysis reveals discrepancies between size and morphological changes due to the corona layer assembly from antibody binding to single nanoparticles versus aggregation or cluster self-assembly into large aggregates. The corona layer formation size increases from 3.9 to 5.1 nm from pH 2 to 6, at pH 7.9, there is incomplete corona formation, whereas at pH 11, there is a corona layer formed of 6.4 nm. These results indicate that the covalent binding process was more efficient at lower pH values; however, aggregation and deactivation of the antibodies were observed. We demonstrate that optimum bioconjugation condition was determined at pH 6 and MES buffer-type by indicators of covalent bonding and stability of the antibody secondary structure using Fourier transform-infrared, the morphological characteristics and corona layer formation using TEM, and low wavelength shifts of ultraviolet-visible after bioconjugation.

Fetuin-A adsorption and stabilization of calcium carbonate nanoparticles in a simulated body fluid.

Fetuin-A is a serum glycoprotein identified as a calcification inhibitor, and a key player in bone formation and human metabolic processes. A study on binding mechanisms of Fetuin-A with calcium carbonate nanoparticles in a simulated body fluid (DMEM) environment is presented. Observed interactions between Fetuin-A and the CaCO3 nanoparticles reveal an initial adsorption process, followed by a stabilization stage, and then a solubilization period for the Fetuin-A/CaCO3 complex. FTIR and XPS are used to monitor functional group and elemental composition changes during the initial adsorption process between Fetuin-A and the CaCO3 nanoparticles. Distinctive Fetuin-A/CaCO3 complex structures-also known as mineralo-protein particles-are imaged with TEM and SEM. DLS and UV-Vis methods are used to further characterize the in situ binding mechanisms. Results of this study can guide the design of complex organic-inorganic hybrid materials, improve current drug delivery methods, and provide insight in monitoring and controlling interactions between Fetuin-A and external calcium ions.