Ln(III) Complexes Embedded in Biocompatible PLGA Nanoparticles as Potential Vis-to-NIR Optical Probes.

In this contribution, we present the spectroscopic study of two NIR emitting hydrophobic heteroleptic (R,R)-YbL1(tta) and (R,R)-NdL1(tta) complexes (with tta = 2-thenoyltrifluoroacetonate and L1 = N,N'-bis(2-(8-hydroxyquinolinate)methylidene)-1,2-(R,R or S,S)-cyclohexanediamine), both in methanol solution and embedded in water dispersible and biocompatible poly lactic-co-glycolic acid (PLGA) nanoparticles. Thanks to their absorption properties in a wide range of wavelengths extending from the UV up to the blue and green visible regions, the emission of these complexes can be effectively sensitized using visible radiation, which is much less harmful to tissues and skin than the UV one. The encapsulation of the two Ln(III)-based complexes in PLGA allows us to preserve their nature, making them stable in water and to test their cytotoxicity on two different cell lines, with the aim of using them in the future as potential bioimaging optical probes.

Fabrication and structural properties of water-dispersible phytosterol using hot melt extrusion.

Hot-melt extrusion (HME) technology was employed to improve water dispersibility of phytosterol (P) using glycerol (G), lecithin (L), and gum arabic (A) as emulsifiers and stabilizers. The structural properties and water dispersibility of HME products were investigated. In contrast to physical mixtures, better water dispersibility and storage stability were observed for HME products, especially P:L:G:A extrudate. These improvements may be mainly associated with decreased crystallinity of phytosterol due to the occurrence of co-crystallization of phytosterol with glycerol during HME process, as confirmed by DSC and XRD data. In addition, HME-induced lecithin-arabic gum reaction products effectively stabilize phytosterol microparticle in aqueous dispersion by providing a steric hindrance. These results suggest that HME could be an effectively and potentially solvent-free technique to produce water-dispersible phytosterol on a large scale.

Design and synthesis of small molecule-conjugated photoaffinity nanoprobes for a streamlined analysis of binding proteins.

We designed and synthesized a set of photoaffinity nanoprobes, which multivalently display a small molecule ligand and a photoreactive group on gold nanoparticles. Due to the typically hydrophobic nature of these two functional groups, a hydrophilic spacer was additionally introduced to co-functionalize the nanoprobes to maintain their dispersibility in aqueous buffer solutions. Photoaffinity labeling studies using the nanoprobes composed of different ratios of three functional groups showed that including high density of the spacer group attenuates crosslinking efficiency. Comparative analysis of the reactivity among three major photoreactive groups suggested that unlike in the context of conventional photoaffinity probes, arylazide group enables the most selective crosslinking of a model small molecule binding protein.

A Tape-Wrapping Strategy towards Electrochemical Fabrication of Water-Dispersible Graphene.

Graphene has achieved mass production via various preparative routes and demonstrated its uniqueness in many application fields for its intrinsically high electron mobility and thermal conductivity. However, graphene faces limitations in assembling macroscopic structures because of its hydrophobic property. Therefore, balancing high crystal quality and good aqueous dispersibility is of great importance in practical applications. Herein, we propose a tape-wrapping strategy to electrochemically fabricate water-dispersible graphene (w-Gr) with both excellent dispersibility (~4.5 mg/mL, stable over 2 months), and well-preserved crystalline structure. A large production rate (4.5 mg/min, six times faster than previous electrochemical methods), high yield (65.4% ≤5 atomic layers) and good processability are demonstrated. A mechanism investigation indicates that the rational design of anode configuration to ensure proper oxidation, deep exfoliation and unobstructed mass transfer is responsible for the high efficiency of this strategy. This simple yet efficient electrochemical method is expected to promote the scalable preparation and applications of graphene.

Highly water dispersible collagen/polyaniline nanocomposites with strong adhesion for electrochromic films with enhanced cycling stability.

Electrochromic materials have attracted extensive attention recently due to their versatile applications in smart windows, displays, antiglare rearview mirrors, and so on. Herein we report a new electrochromic composite prepared from collagen and polyaniline (PANI) through a self-assembly assisted co-precipitation method. The introduction of hydrophilic collagen macromolecules into PANI nanoparticles makes the collagen/PANI (C/PANI) nanocomposite obtain excellent dispersibility in water, which provides good environmental-friendly solution processability. Furthermore, the C/PANI nanocomposite exhibits excellent film-forming properties and adhesion to the ITO glass matrix. The resulting electrochromic film of the C/PANI nanocomposite displays significantly improved cycling stability compared with the pure PANI film after 500 coloring-bleaching cycles. On the other hand, the composite films also exhibit yellow, green and blue polychromatic properties at different applied voltages and high average transmittance at the bleaching state. The C/PANI electrochromic material illustrates scaling potential for the application of electrochromic devices.

Janus effects of NaCl on structure of egg yolk granules.

Egg yolk granules are supramolecular assembly of high-density lipoproteins and phosvitin driven by calcium bridges. However, applications of granules are severely restricted by the large particle size and poor water dispersibility. This study revealed the Janus effects of NaCl on structure of granules at varied pH values. Addition of 0.3-0.5 M NaCl led to the dissociation of at pH 5.0-7.0. At pH 5.0-10.0, dissociated granules demonstrated good colloidal stability with NaCl because of the adsorption of highly hydrated Na+ and Ca2+, which provided strong hydration repulsion when electrostatic repulsion was screened. In contrast, at pH 2.0 and 3.0, dissociated granules were positively charged with adsorption of poorly hydrated Cl- as counterions. Cl- failed to give sufficient hydration repulsion, leading to the phase separation with 0.3-0.5 M NaCl. Similar effects have been also found in LiCl, KCl, and CsCl, but Li+ might be less effective to disrupt calcium bridges.

Self-assembly CuO-loaded nanocomposite involving functionalized DNA with dihydromyricetin for water-based efficient and controllable antibacterial action.

With the antibiotic crisis intensifies, the defense and treatment of pathogen infections in safe and effective fashion has become a critical issue. Herein, we report a novel and advanced type of sterilization agent designed via the functionalization DNA nanocarriers based on dihydromyricetin and CuO-loaded nanoparticles (DNA/DMY-CuO). Firstly, a pure dihydromyricetin (DMY) isolated from Ampelopsis grossedentata is used as a bridge to the stimulate the construction of DNA cross-linking networks by hydrogen bonding. Subsequently, a 3D spherical CuO-loaded nanocomposite (204.39 nm) is customized using the DNA/DMY network as a biological template through a simple coordination-assisted self-assembly method, which exhibits a high dispersibility, water-solubility and physiological stability. The reversible physical interactions in nanocarriers allows the selective separation and automatic release of CuO NPs from DNA/DMY-CuO in neutral and wound exudate environments, thereby extending the survival period of CuO NPs by nearly 24 h. Meanwhile, the nanocarriers system relied on the strong binding ability of DMY to the outer membrane of Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) achieves controlled drug delivery onto the pathogen wall. The advanced antibacterial action of DNA/DMY-CuO also reflected in membrane destruction, cytoplasmic constituent leakages and ATP synthetic pathway cessation, thereby halting cytosolic metalloregulatory mechanisms and minimizing drug-resistant bacteria. In summary, such multi-functional CuO-loaded nanocomposite provides a water-dispersibility, controllable, low cytotoxicity and long-effective platform to address the ever-growing threats of bacterial infections.

Water-Dispersible Porous Aromatic Frameworks with Quasi-Amino Acid Structures via N-H Insertion Reactions.

As a class of materials with large specific surface area and chemical stability, porous aromatic frameworks (PAFs) have attracted much attention in the fields of gas adsorption, separation, and catalysis. However, synthetic methods for PAFs have been limited to a few coupling reactions, and PAF powders were usually obtained with a diameter of micrometer size. Here, we demonstrate an efficient N-H insertion reaction of diazoesters in the synthesis of PAFs with a diameter <200 nm. The established polymerization can be performed at room temperature, and four PAFs with different skeletons and composition can be obtained in high yields. The prepared PAFs have appreciable thermal and chemical stabilities. Because of the presence of ester groups in the backbone, the prepared PAFs with α-phenylglycine fragments can be easily obtained through the successive hydrolysis of the ester groups. The synthesized PAFs bearing phenylglycine moieties exhibit good water dispersibility and low cytotoxicity. We further show the potential of these PAFs in drug loading and photodynamic therapy.

Water-dispersible, biocompatible and fluorescent poly(ethylene glycol)-grafted cellulose nanocrystals.

Fluorescent nanoprobe with good water dispersibility was synthesized by the coupling of fluorescent 1,8-naphthalimide dye (NANI) as well as biocompatible poly (ethylene glycol) (PEG) to cellulose nanocrystals (CNC). FTIR, TGA and XPS analysis confirmed the successful covalent conjugation of NANI and PEG. The rod-like morphology of CNC was generally retained after two-step successive grafting of NANI and PEG. The contact angle and transmittance measurements showed that the grafted PEG brushes improve the hydrophilicity of fluorescent CNC probes and their dispersibility in high-concentration NaCl solutions. The fluorescent CNC probe had good biocompatibility and was successfully used for the bioimaging of Hela cells in physiological environment at high salt concentration. Laser confocal microscopy showed that the fluorescent CNC probe can penetrate the cell membrane and disperse uniformly in the cell with good biocompatibility. The fluorescent CNC probe with nanometer size, strong fluorescence emission and high salt-tolerance possess potential application in biomedical field.

Synthesis, Characterization, and Evaluation of Genistein-Loaded Zein/Carboxymethyl Chitosan Nanoparticles with Improved Water Dispersibility, Enhanced Antioxidant Activity, and Controlled Release Property.

Genistein is one of major isoflavones derived from soybean products and it is believed to have beneficial effects on human health. However, its low water-solubility and poor oral bioavailability severely hamper its use as a functional food ingredient or for pharmaceutical industry. In this study, zein and zein/carboxymethyl chitosan (CMCS) nanoparticles were prepared to encapsulate genistein using a combined liquid-liquid phase separation method. The physicochemical properties of fabricated nanoparticles were characterized by dynamic light scattering (DLS), atomic force microscopy (AFM), and Fourier transform infrared spectroscopy (FTIR). The results demonstrated that genistein encapsulated with zein nanoparticles significantly improved its water dispersibility, antioxidant activity in the aqueous phase, and photostability against UV light. Moreover, genistein encapsulated in zein nanoparticles showed a sustained release property. Furthermore, it was found that encapsulation efficiency of genistein was significantly enhanced after CMCS coating, and this effect was more pronounced after the complex nanoparticles cross-linked with calcium ions when compared with the use of zein as a single encapsulant. In addition, compared to zein nanoparticles without biopolymer coating, CMCS coating significantly enhanced the thermal and storage stability of the formed nanoparticles, and delayed the release of genistein. A schematic diagram of zein and zein/carboxymethyl chitosan (CMCS) nanoparticles formation mechanism for encapsulation of genistein was proposed. According to the results of the current study, it could be concluded that encapsulation of genistein in zein/CMCS nanoparticles is a promising approach to improve its water dispersibility, antioxidant activity, photostability against UV light and provide controlled release for food/pharmaceutical applications.