Effect of (3-aminopropyl)triethoxysilane on dissolution of silica nanoparticles synthesized via reverse micro emulsion.

Silica nanomaterials have been studied based on their potential applications in a variety of fields, including biomedicine and agriculture. A number of different molecules have been condensed onto silica nanoparticles' surfaces to present the surface chemistry needed for a given application. Among those molecules, (3-aminopropyl)triethoxysilane (APS) is one of the most commonly applied silanes used for nanoparticle surface functionalization to achieve charge reversal as well as to enable cargo loading. However, the colloidal stability of APS-functionalized silica nanoparticles has not been thoroughly studied, which can be problematic when the high reactivity of amine groups is considered. In this study, four different types of silica nanoparticles with varied location of added APS have been prepared via a reverse micro emulsion process, and their colloidal stability and dissolution behavior have been investigated. Systematic characterization has been accomplished using transmission electron microscopy (TEM), silicomolybdic acid (SMA) spectrophotometric assay, nitrogen adsorption-desorption surface area measurement, and aerosol ion mobility-mass spectrometry to track the nanoparticles' physical and chemical changes during dissolution. We find that when APS is on the interior of the silica nanoparticle, it facilitates dissolution, but when APS is condensed both on the interior and exterior, only the exterior siloxane bonds experience catalytic hydrolysis, and the interior dissolution is dramatically suppressed. The observation and analyses that silica nanoparticles show different hydrolysis behaviors dependent on the location of the functional group will be important in future design of silica nanoparticles for specific biomedical and agricultural applications.

Silica Nanoparticle Dissolution Rate Controls the Suppression of Fusarium Wilt of Watermelon (Citrullus lanatus).

Projected population increases over the next 30 years have elevated the need to develop novel agricultural technologies to dramatically increase crop yield, particularly under conditions of high pathogen pressure. In this study, silica nanoparticles (NPs) with tunable dissolution rates were synthesized and applied to watermelon (Citrullus lanatus) to enhance plant growth while mitigating development of the Fusarium wilt disease caused by Fusarium oxysporum f. sp. niveum. The hydrolysis rates of the silica particles were controlled by the degree of condensation or the catalytic activity of aminosilane. The results demonstrate that the plants treated with fast dissolving NPs maintained or increased biomass whereas the particle-free plants had a 34% decrease in biomass. Further, higher silicon concentrations were measured in root parts when the plants were treated with fast dissolving NPs, indicating effective silicic acid delivery. In a follow-up field study over 2.5 months, the fast dissolving NP treatment enhanced fruit yield by 81.5% in comparison to untreated plants. These findings indicate that the colloidal behavior of designed nanoparticles can be critical to nanoparticle-plant interactions, leading to disease suppression and plant health as part of a novel strategy for nanoenabled agriculture.

Microstructures and pharmaceutical properties of ferulic acid agglomerates prepared by different spherical crystallization methods.

Spherical agglomerates of an active pharmaceutical ingredient, ferulic acid (FA), were prepared using four different spherical crystallization methods, i.e., quasi-emulsion solvent diffusion (QESD), anti-solvent, pH shift, and the direct method. Both the as-received FA and spherical agglomerates were characterized in terms of specific surface area (SSA), primary crystal shape and size, granule morphology and size, powder flowability, tabletability at two distinct speeds, and dissolution (both powder and tablet). Results showed that the microstructure, which is affected by size, shape, and packing of primary crystals, was the key that determined the flowability, tabletability and dissolution. The QESD powder exhibited the best flowability and tabletability. Both powder and tablet dissolution of FA followed the order of as-received > QESD > anti-solvent > pH shift, which was consistent with the order of the surface area exposed to the dissolution medium and not SSA. Moreover, compression reduced differences in the rates of dissolution of FA powders due to the size reduction of agglomerates by fragmentation.

Preparation of Colloidally Stable Positively Charged Hollow Silica Nanoparticles: Effect of Minimizing Hydrolysis on ζ Potentials.

Silica nanoparticles have received great attention as versatile nanomaterials in many fields such as drug delivery, sensing, and imaging due to their physical and chemical flexibility. Specifically, the silanol groups at the surface of silica nanoparticles have enabled various surface modifications and functionalization to tailor the nanoparticles for each application. Chemical tailoring to switch from negative to positive surface charge has been one important strategy to enhance cell internalization and biodistribution of the nanoparticles. However, efficient surface charge modification that is sustained upon dispersion is difficult to achieve and has not been well characterized though it can be a critical requirement for successful nanoparticle performance. In this study, solid spherical silica nanoparticles and hollow spherical silica nanoparticles around 45 nm in diameter were synthesized, both possessing tunable positive ζ potentials in aqueous colloidal suspension, to investigate the relationship between time-dependent ζ potential changes and their morphologies. A set of three different particles showing varied ζ potentials of approximately 5, 20, and >30 mV in both morphologies were prepared, and their colloidal surface electric potential fluctuations were measured. These studies reveal that the hollow morphologies are much more effectively able to maintain positive ζ potentials for 7 days of aqueous incubation, whereas the magnitude of the ζ potential of the solid silica spheres decreases uncontrollably, largely due to hydrolysis of the interior siloxane bonds, resulting in adsorption of the released silicic acid onto the nanoparticle surface.

Stabilization of Silver and Gold Nanoparticles: Preservation and Improvement of Plasmonic Functionalities.

Noble metal nanoparticles have been extensively studied to understand and apply their plasmonic responses, upon coupling with electromagnetic radiation, to research areas such as sensing, photocatalysis, electronics, and biomedicine. The plasmonic properties of metal nanoparticles can change significantly with changes in particle size, shape, composition, and arrangement. Thus, stabilization of the fabricated nanoparticles is crucial for preservation of the desired plasmonic behavior. Because plasmonic nanoparticles find application in diverse fields, a variety of different stabilization strategies have been developed. Often, stabilizers also function to enhance or improve the plasmonic properties of the nanoparticles. This review provides a representative overview of how gold and silver nanoparticles, the most frequently used materials in current plasmonic applications, are stabilized in different application platforms and how the stabilizing agents improve their plasmonic properties at the same time. Specifically, this review focuses on the roles and effects of stabilizing agents such as surfactants, silica, biomolecules, polymers, and metal shells in colloidal nanoparticle suspensions. Stability strategies for other types of plasmonic nanomaterials, lithographic plasmonic nanoparticle arrays, are discussed as well.

Effect of Silica Supports on Plasmonic Heating of Molecular Adsorbates as Measured by Ultrafast Surface-Enhanced Raman Thermometry.

Plasmonic materials show great potential for selective photocatalysis under relatively mild reaction conditions. However, the catalytic activity of these plasmonic catalysts can also depend upon the support material that stabilizes the catalysts, where the composition of the catalytic support may change the overall photocatalytic efficiency and yield. It is unknown how changes in the support material may change the plasmon-driven photocatalysis, which may be initiated by plasmon-derived hot carriers, localized heating, or enhanced electromagnetic fields. Herein, we probe the effects of catalytic supports on heating in plasmon-driven catalysis by examining various gold nanoparticle oxide systems. We use ultrafast surface-enhanced Raman thermometry to measure the effective temperature, equivalent to the vibrational kinetic energy, of reporter molecules located between plasmonic gold nanostructures and local environments ranging from ligands to mesoporous silica shells to silica shells. Upon photoexcitation, the transient effective temperature, equivalent to the energy deposited into a vibrational mode, of adsorbed molecules on the silica-coated samples increases, and the energy quickly dissipates within 3 ps. However, the baseline effective temperature that arises from the surface-enhanced Raman spectroscopy probing process depends upon the encapsulant, where the energy deposition differs by 200-300 K between the ligand-coated (citrate or CTAB) and the silica-coated samples. Adsorbates surrounded by a silica shell experience significantly higher effective temperatures than the adsorbates surrounded by ligands or solvent, likely because of the differing effective heat capacities of these media. Taken together, this work shows that a silica support impacts the localized heating of molecular adsorbates on the gold surface and may play a role in enhanced plasmonic photocatalysis because of increased thermal contributions.

Molecular Affinity Agents for Intrinsic Surface-Enhanced Raman Scattering (SERS) Sensors.

Research at the interface of synthetic materials, biochemistry, and analytical techniques has enabled sensing platforms for applications across many research communities. Herein we review the materials used as affinity agents to create surface-enhanced Raman spectroscopy (SERS) sensors. Our scope includes those affinity agents (antibody, aptamer, small molecule, and polymer) that facilitate the intrinsic detection of targets relevant to biology, medicine, national security, environmental protection, and food safety. We begin with an overview of the analytical technique (SERS) and considerations for its application as a sensor. We subsequently describe four classes of affinity agents, giving a brief overview on affinity, production, attachment chemistry, and first uses with SERS. Additionally, we review the SERS features of the affinity agents, and the analytes detected by intrinsic SERS with that affinity agent class. We conclude with remarks on affinity agent selection for intrinsic SERS sensing platforms.

Characterization of Magnetic Nanoparticles in Biological Matrices.

This Feature describes several methods for the characterization of magnetic nanoparticles in biological matrices such as cells and tissues. The Feature focuses on sample preparation and includes several case studies where multiple techniques were used in conjunction.