A New Insight into Growth Mechanism and Kinetics of Mesoporous Silica Nanoparticles by in Situ Small Angle X-ray Scattering.

The growth mechanism and kinetics of mesoporous silica nanoparticles (MSNs) were investigated for the first time by using a synchrotron time-resolved small-angle X-ray scattering (SAXS) analysis. The synchrotron SAXS offers unsurpassed time resolution and the ability to detect structural changes of nanometer sized objects, which are beneficial for the understanding of the growth mechanism of small MSNs (∼20 nm). The Porod invariant was used to quantify the conversion of tetraethyl orthosilicate (TEOS) in silica during MSN formation, and the growth kinetics were investigated at different solution pH and temperature through calculating the scattering invariant as a function of reaction time. The growth of MSNs was found to be accelerated at high temperature and high pH, resulting in a higher rate of silica formation. Modeling SAXS data of micelles, where a well-defined electrostatic interaction is assumed, determines the size and shape of hexadecyltrimethylammonium bromide (CTAB) micelles before and after the addition of TEOS. The results suggested that the micelle size increases and the micelle shape changes from ellipsoid to spherical, which might be attributed to the solubilization of TEOS in the hydrophobic core of CTAB micelles. A new "swelling-shrinking" mechanism is proposed. The mechanism provides new insights into understanding MSN growth for the formation of functional mesoporous materials exhibiting controlled morphologies. The SAXS analyses were correlated to the structure of CTAB micelles and chemical reaction of TEOS. This study has provided critical information to an understanding of the growth kinetics and mechanism of MSNs.

New insight into non-isothermal crystallization of PVA-graphene composites.

The melt crystallization of poly(vinyl alcohol) (PVA) and PVA composites has been a controversial subject due to inconclusive evidence and different opinions for its decomposition during crystallization. Using graphene as a model, the melt crystallization of PVA and PVA-graphene composites occurring during single-cycle and multiple-cycle non-isothermal annealing processes was systematically analyzed using different characterization techniques. The results obtained using single-cycle non-isothermal annealing indicated that the entire crystallization process took place through two main stages. The graphene in the PVA matrix regulates the nucleation and crystal growth manner of the PVA, yet resulting in retardation of the entire crystallization. The FTIR and Raman spectroscopic results particularly demonstrated that the annealing process not only improved the crystallinity but also led to clear decomposition in PVA and PVA-graphene composites, such as the elimination of hydroxyl groups and the production of C=C double bonds. The newly produced C=C double bonds were found to be responsible for the retardation of PVA macromolecule crystallization and the breaking of hydrogen bonds among the hydroxyl groups in the PVA chains. In addition, the morphological observation and multi-cycle non-isothermal crystallization further confirmed the existence of decomposition based on the surface damage as well as decreased crystallization enthalpy and crystallization peak temperature. Therefore, the non-isothermal crystallizations of the pure PVA and the PVA-graphene composites were in fact the combination of non-isothermal crystallization and non-isothermal degradation processes.

Oxidized Chitosan-Tobramycin (OCS-TOB) Submicro-Fibers for Biomedical Applications.

Chitosan (CS) is a biodegradable, biocompatible, and non-toxic natural amino-poly-saccharide with antibacterial ability, owing to its positively charged amino groups. However, the low charge density leads to poor antibacterial efficiency which cannot meet the biomedical application requirements. In this study, Tobramycin (TOB) was grafted onto the backbone of oxidized chitosan (OCS) to synthesize oxidized chitosan-tobramycin (OCS-TOB). FTIR, 1H NMR and elemental analysis results demonstrated that OCS-TOB was successfully synthesized. OCS-TOB/PEO composite fibrous materials were produced by a self-made centrifugal spinning machine. In vitro experiments showed that cells proliferated on the submicro-fibrous OCS-TOB/PEO of appropriate concentration, and the antibacterial ability of OCS-TOB was much improved, compared with pristine CS. The results demonstrated that OCS-TOB/PEO nanofibrous materials could potentially be used for biomedical applications.

Multi-Functional Core-Shell Nanofibers for Wound Healing.

Core-shell nanofibers have great potential for bio-medical applications such as wound healing dressings where multiple drugs and growth factors are expected to be delivered at different healing phases. Compared to monoaxial nanofibers, core-shell nanofibers can control the drug release profile easier, providing sustainable and effective drugs and growth factors for wound healing. However, it is challenging to produce core-shell structured nanofibers with a high production rate at low energy consumption. Co-axial centrifugal spinning is an alternative method to address the above limitations to produce core-shell nanofibers effectively. In this study, a co-axial centrifugal spinning device was designed and assembled to produce core-shell nanofibers for controlling the release rate of ibuprofen and hEGF in inflammation and proliferation phases during the wound healing process. Core-shell structured nanofibers were confirmed by TEM. This work demonstrated that the co-axial centrifugal spinning is a high productivity process that can produce materials with a 3D environment mimicking natural tissue scaffold, and the specific drug can be loaded into different layers to control the drug release rate to improve the drug efficiency and promote wound healing.

Substrate-Independent, Regenerable Anti-Biofouling Coating for Polymeric Membranes.

Biofouling is a common but significant issue in the membrane process as it reduces permeate flux, increases energy costs, and shortens the life span of membranes. As an effective antibacterial agent, a small amount of silver nanoparticles (AgNPs) immobilized on membrane surfaces will alleviate the membrane from biofouling. However, loading AgNPs on the membrane surface remains a challenge due to the low loading efficiency or the lack of bonding stability between AgNPs and the membrane surface. In this study, a substrate-independent method is reported to immobilize silver nanoparticles on polymeric membrane surfaces by firstly modifying the membrane surface with functional groups and then forming silver nanoparticles in situ. The obtained membranes had good anti-biofouling properties as demonstrated from disk diffusion and anti-biofouling tests. The silver nanoparticles were stably immobilized on the membrane surfaces and easily regenerated. This method is applicable to various polymeric micro-, ultra-, nano-filtration and reverse osmosis (RO) membranes.

Functional Nanofibrous Biomaterials of Tailored Structures for Drug Delivery-A Critical Review.

Nanofibrous biomaterials have huge potential for drug delivery, due to their structural features and functions that are similar to the native extracellular matrix (ECM). A wide range of natural and polymeric materials can be employed to produce nanofibrous biomaterials. This review introduces the major natural and synthetic biomaterials for production of nanofibers that are biocompatible and biodegradable. Different technologies and their corresponding advantages and disadvantages for manufacturing nanofibrous biomaterials for drug delivery were also reported. The morphologies and structures of nanofibers can be tailor-designed and processed by carefully selecting suitable biomaterials and fabrication methods, while the functionality of nanofibrous biomaterials can be improved by modifying the surface. The loading and releasing of drug molecules, which play a significant role in the effectiveness of drug delivery, are also surveyed. This review provides insight into the fabrication of functional polymeric nanofibers for drug delivery.

High Efficiency Fabrication of Chitosan Composite Nanofibers with Uniform Morphology via Centrifugal Spinning.

While electrospinning has been widely employed to spin nanofibers, its low production rate has limited its potential for industrial applications. Comparing with electrospinning, centrifugal spinning technology is a prospective method to fabricate nanofibers with high productivity. In the current study, key parameters of the centrifugal spinning system, including concentration, rotational speed, nozzle diameter and nozzle length, were studied to control fiber diameter. An empirical model was established to determine the final diameters of nanofibers via controlling various parameters of the centrifugal spinning process. The empirical model was validated via fabrication of carboxylated chitosan (CCS) and polyethylene oxide (PEO) composite nanofibers. DSC and TGA illustrated that the thermal properties of CCS/PEO nanofibers were stable, while FTIR-ATR indicated that the chemical structures of CCS and PEO were unchanged during composite fabrication. The empirical model could provide an insight into the fabrication of nanofibers with desired uniform diameters as potential biomedical materials. This study demonstrated that centrifugal spinning could be an alternative method for the fabrication of uniform nanofibers with high yield.

In Situ SAXS Measurement and Molecular Dynamics Simulation of Magnetic Alignment of Hexagonal LLC Nanostructures.

The alignment of nanostructures in materials such as lyotropic liquid crystal (LLC) templated materials has the potential to significantly improve their performances. However, accurately characterising and quantifying the alignment of such fine structures remains very challenging. In situ small angle X-ray scattering (SAXS) and molecular dynamics were employed for the first time to understand the hexagonal LLC alignment process with magnetic nanoparticles under a magnetic field. The enhanced alignment has been illustrated from the distribution of azimuthal intensity in the samples exposed to magnetic field. Molecular dynamics simulations reveal the relationship between the imposed force of the magnetic nanoparticles under magnetic field and the force transferred to the LLC cylinders which leads to the LLC alignment. The combinational study with experimental measurement and computational simulation will enable the development and control of nanostructures in novel materials for various applications.

Superhydrophobic and Superoleophilic Micro-Wrinkled Reduced Graphene Oxide as a Highly Portable and Recyclable Oil Sorbent.

The potential of superhydrophobic and superoleophilic microwrinkled reduced graphene oxide (MWrGO) structures is here demonstrated for oil spill cleanup. The impact of the thickness of MWrGO films on the sorption performance of three different oils was investigated. Water contact angles across the MWrGO surfaces were found to exceed 150°, while oil could be easily absorbed by the microwrinkled structures of MWrGO within seconds after contact. Although the oil surface diffusion rate was not found to be dependent on the thickness of the graphene oxide films, the oil sorption capacity was the largest with the thinner MWrGO films due to the high surface area resulting from their fine surface texture. Furthermore, the composite films can be repeatedly used for at least 20 oil sorption-removal cycles without any notable loss in selectivity and uptake capacity. These MWrGO/elastomer composite films could be applied as a potential candidate material for future oil spill cleanup.

Functionalized mesoporous silica nanoparticles with redox-responsive short-chain gatekeepers for agrochemical delivery.

The controlled release of salicylic acid (SA), a key phytohormone, was mediated by using a novel decanethiol gatekeeper system grafted onto mesoporous silica nanoparticles (MSNs). The decanethiol was conjugated only to the external surfaces of the MSNs through glutathione (GSH)-cleavable disulfide linkages and the introduction of a process to assemble gatekeepers only on the outer surface so that the mesopore area can be maintained for high cargo loading. Raman and nitrogen sorption isotherm analyses confirmed the successful linkage of decanethiol to the surface of MSNs. The in vitro release of SA from decanethiol gated MSNs indicated that the release rate of SA in an environment with a certain amount of GSH was significantly higher than that without GSH. More importantly, in planta experiments showed the release of SA from decanethiol gated MSNs by GSH induced sustained expression of the plant defense gene PR-1 up to 7 days after introduction, while free SA caused an early peak in PR-1 expression which steadily decreased after 3 days. This study demonstrates the redox-responsive release of a phytohormone in vitro and also indicates the potential use of MSNs in planta as a controlled agrochemical delivery system.

Amine Enrichment of Thin-Film Composite Membranes via Low Pressure Plasma Polymerization for Antimicrobial Adhesion.

Thin-film composite membranes, primarily based on poly(amide) (PA) semipermeable materials, are nowadays the dominant technology used in pressure driven water desalination systems. Despite offering superior water permeation and salt selectivity, their surface properties, such as their charge and roughness, cannot be extensively tuned due to the intrinsic fabrication process of the membranes by interfacial polymerization. The alteration of these properties would lead to a better control of the materials surface zeta potential, which is critical to finely tune selectivity and enhance the membrane materials stability when exposed to complex industrial waste streams. Low pressure plasma was employed to introduce amine functionalities onto the PA surface of commercially available thin-film composite (TFC) membranes. Morphological changes after plasma polymerization were analyzed by SEM and AFM, and average surface roughness decreased by 29%. Amine enrichment provided isoelectric point changes from pH 3.7 to 5.2 for 5 to 15 min of plasma polymerization time. Synchrotron FTIR mappings of the amine-modified surface indicated the addition of a discrete 60 nm film to the PA layer. Furthermore, metal affinity was confirmed by the enhanced binding of silver to the modified surface, supported by an increased antimicrobial functionality with demonstrable elimination of E. coli growth. Essential salt rejection was shown minimally compromised for faster polymerization processes. Plasma polymerization is therefore a viable route to producing functional amine enriched thin-film composite PA membrane surfaces.

Fabrication of Meso-Porous Sintered Metal Thin Films by Selective Etching of Silica Based Sacrificial Template.

Meso-porous metal materials have enhanced surface energies offering unique surface properties with potential applications in chemical catalysis, molecular sensing and selective separation. In this paper, commercial 20 nm diameter metal nano-particles, including silver and copper were blended with 7 nm silica nano-particles by shear mixing. The resulted powders were cold-sintered to form dense, hybrid thin films. The sacrificial silica template was then removed by selective etching in 12 wt% hydrofluoric acid solutions for 15 min to reveal a purely metallic meso-porous thin film material. The impact of the initial silica nano-particle diameter (7-20 nm) as well as the sintering pressure (5-20 ton·m-2) and etching conditions on the morphology and properties of the final nano-porous thin films were investigated by porometry, pyknometery, gas and liquid permeation and electron microscopy. Furthermore, the morphology of the pores and particle aggregation during shear mixing were assessed through cross-sectioning by focus ion beam milling. It is demonstrated that meso-pores ranging between 50 and 320 nm in average diameter and porosities up to 47% can be successfully formed for the range of materials tested.