From colloidal nanoparticles in non-polar solvents to 3D microstructures: a new paradigm in Convective Self-Assembly.

Formulation, process, and storage strategies for lyophilizates of lipophilic nanoparticulate systems established based on the two models paliperidone palmitate and solid lipid nanoparticles

Fluorescence technology has considerably advanced, enabling the observation, and elucidation of various behavioral mechanisms. Despite these advancements, photobleaching remains a major challenge, inhibiting sustained fluorescence emission and adversely affecting fluorescence imaging observations. In this study, we used a redox method to synthesize two types of metal nanoparticles (NPs), specifically silver (Ag), and gold (Au) NPs. We explored the photobleaching effects of fluorescein sodium salt (FSS) at different concentrations and investigated NPs with surface spacers of varying polyethylene glycol (PEG) lengths. The results indicated that the two types of NPs effectively enhanced the fluorescence signal of FSS when they were combined with PEG spacers having lengths of 5.2, 6.6, 9.1, and 20.8 nm (PEG4K, PEG6K, PEG10K, and PEG40K, respectively). Among all NPs, Ag‐PEG4K exhibited the strongest metal‐enhanced fluorescence effect. In addition, the two types of NPs were able to delay photobleaching. Although their effects differed depending on spacer length, no positive or negative correlation was observed between their effectiveness and spacer length. Among all NPs, Au‐PEG4K was the most effective in delaying photobleaching. Overall, our findings indicate that the combination of metal NPs with PEG spacers mitigates the degree of photobleaching, making this approach promising for extended fluorescence imaging observations.

Hydroxyapatite nano and microparticles: Correlation of particle properties with cytotoxicity and biostability

Core–shell types of polymer-based nanoparticles (NPs) are attractive from the standpoint of integrating the key features of core and shell into hybrid or composite materials, such as controllable particle size, surface functionality and entrapment of particular particles. The focus of core–shell design over the years has evolved toward more innovative, simple and cost-effective methods. This chapter provides an overview of recent progress in the fabrication methodologies and functional modulations of polymer-based core–shell NPs in colloid and materials science. Discussion and comparisons are presented, along with a summary and outlook of these methods for core–shell hybrid architecture.

Zein is major nitrogen storage protein that accounts for nearly half of the protein content of the corn grain. As a byproduct of starch and ethanol processing, it is generally recognized as safe (GRAS) and soluble in up to 70% ethanol. Historically, zein has been used for films and coatings. However, usage of the corn protein has diminished in recent years. New advances in food nanotechnology has renewed interest in zein. By forming the protein into stable nanoparticles capable of being dispersed in aqueous solution, zein can be used in many applications ranging from improving stability and digestion of functional ingredients or active biodegradable packaging. Developing novel applications for this protein would then add value to a waste product during the processing of corn.<br>The formation of hydrophobic zein nanoparticles (ZNPs) would allow for easier dispersion in aqueous systems without further modification to increase hydrophilicity. However, their dispersibility and subsequent stability in aqueous systems is important for its functionality in food. Addition of sufficient ι-carrageenan (ι-CGN) prevented aggregation in the pH range of 5.25 to 6.75 and limited aggregation at pH 7.0. Enhanced stability was attributed to the adhesion of ι-CGN to the nanoparticle surface, as the ZNPs surface charge became significantly negative with introduction of ι-CGN. These particles remained stable for up to 30 days with significantly lower turbidity and greater resistance to gravitational separation when compared to ZNPs alone.<br>Lutein was encapsulated in zein nanoparticles, and the bioaccessibility was determined by quantifying lutein content after exposure to in vitro gastric and intestinal conditions. It was found that ZNPs provided a protective environment for lutein in aqueous dispersions and would release the carotenoid into the small intestine by rapid breakdown of ZNP structure during intestinal digestion. However, the process or residual components must have limited uptake of lutein into mixed micelles. ZNPs can be a promising encapsulating agent to improve the digestive stability of lutein.<br>Composite films composed of methylcellulose (MC) and zein nanoparticles (ZNPs) were prepared as a potential biodegradable alternative for synthetic packaging. The effects of ZNP aggregation on mechanical and moisture barrier properties as affected by drying temperature, pH, and stabilizers were tested. The phase separation of composite films was determined to be detrimental to both its mechanical and moisture barrier properties. The drying temperature, pH, and composition of the solvent casting solution all affected the distribution of ZNPs dispersed in MC films. Drying films at 23°C or setting the pH to 6.5 resulted in ZNP aggregation and weaker, brittle films that were poor moisture barriers. The presence of CGN was able to provide stability to ZNPs at both pH 4 and 6.5, thus improving its mechanical and moisture barrier properties.

Aqueous suspensions of dendronized iron oxide nanoparticles (NPs) have been obtained after functionalization, with two types of dendrons, of NPs synthesized either by coprecipitation (leading to naked NPs in water) or by thermal decomposition (NPs in situ coated by oleic acid in an organic solvent). Different grafting strategies have been optimized depending on the NPs synthetic method. The size distribution, the colloidal stability in isoosmolar media, the surface complex nature as well as the preliminary biokinetic studies performed with optical imaging, and the contrast enhancement properties evaluated through in vitro and in vivo MRI experiments, have been compared as a function of the nature of both dendrons and NPs. All functionalized NPs displayed good colloidal stability in water, however the ones bearing a peripheral carboxylic acid function gave the best results in isoosmolar media. Whereas the grafting rates were similar, the nature of the surface complex depended on the NPs synthetic method. The in vitro contrast enhancement properties were better than commercial products, with a better performance of the NPs synthesized by coprecipitation. On the other hand, the NPs synthesized by thermal decomposition were more efficient in vivo. Furthermore, they both displayed good biodistribution with renal and hepatobiliary elimination pathways and no consistent RES uptake.

Summary The operational use of nanoparticles (NPs) in drilling and completion fluids is still limited at the present time, in part because of a lack of consistent evidence for and clarification of NP interactions with rock formations, formation fluid, and other fluid additives. For instance, previous fluids research emphasized that NPs bring about pore plugging, which reduces pressure transmission and, in turn, fluid inflow, into the shale pore matrix, which ultimately helps stabilize the borehole. However, it is difficult to understand how pore plugging might be accomplished in the absence of any substantial filtration in shales, considering that the minimal permeability of shales does not allow for any appreciable Darcy flow. This paper addresses the crucial question: “How, when, and why do NPs plug shale pore throats?” Zeta-potential (ZP) measurements were carried out on aqueous NP dispersions and on intact thin shale sections exposed to nanofluids to determine the degree of interaction behavior between NPs and shale. The experimental data were then used to calculate Derjaguin-Landau-Verwey-Overbeek (DLVO) curves (describing the force between charged surfaces interacting through a liquid medium) to determine if the total potential energy was sufficient for NPs to diffuse through the repellent barrier and attach to the shale surface. Calculated DLVO curves were used to demonstrate the NPs ability to contribute to borehole stability, but did not directly correlate the effects the NPs had on shale stability. Experiments, including pore pressure-transmission tests (PTTs), which measure fluid pressure penetration in shale, and modified thick-walled-cylinder (TWC) collapse tests, which explore the influence of NPs on the collapse pressure of shale samples, were conducted to directly investigate the effects of NPs on borehole stability in shale. Our investigation showed that NPs can reduce fluid pressure penetration and delay borehole collapse in shale, but only under certain conditions. Electrostatic/electrodynamic interaction between NPs and shale surfaces, governed by DLVO forces, is the main mechanism that leads to pore-throat plugging, reducing pressure transmission, which in turn benefits borehole stability by slowing down near-wellbore pore-pressure elevation and effective-stress reduction. For Mancos Shale, 20-nm anionic nanosilica particles were effective in partially plugging the pore-throat system, depending on the pH of the nanofluid, which affects the surface potential and ZP of both NPs and shale. Furthermore, cationic nanosilica showed better results for pore-plugging capabilities than the anionic nanosilica. Our findings lead to interesting challenges for the practical field application of NP-based drilling fluids for borehole stability, given that efficacy depends on the specific type of shale; the specific type, size, and concentration of NP; the interaction between NPs and shale; and external factors, such as pH, salinity, and temperature. Therefore, NP use for practical shale stabilization requires a dedicated, thoroughly engineered solution for each particular field application, and is unlikely to be “one size fits all.”

The water in oil microemulsion or reverse micelle has been used in the past two decades for the synthesis of many different types of nanoparticles. The nano meter sized aqueous cores of the reverse micelle provide an appropriate stabilized environment for the production of nanoparticles of fairly uniform size, through chemical reactions occurring in the core and it also acts as steric stabilizers to inhibit the aggregation of nanoparticles formed. The water in oil microemulsion has been used to synthesize different types of core nano particles (metals, and semiconductors) as well as core-shell/ composite nanoparticles. This article describes the preparation techniques, and the various techniques used to characterize these core and core-shell nanoparticles as well as insights in to the effects of various process parameters on the terminal particle size. A brief review of our modeling work based on stochastic population balance is also presented, which can be used to describe the formation of both core and coreshell nanoparticles. In addition, we have also presented a brief review of the work on the synthesis of anisotropic nanostructures like nanorods and nanowires by templating against surfactant micelles and reverse micelles. Some findings of our work, addressing the engineering issues, such as possibility of reusing surfactant and organic phases are also included in this article.

Colloidal nanoparticle could be used for recognition location of tumors and cancer tissue. A simulation of molecular dynamic for colloidal silver nanoparticles (Ag NPs) based on density functional theory (DFT) potential parametrization with different sizes in 1-ethyl-3-methylimidazolium hexafluorophosphate [EMim][PF6] ionic liquid was performed. Then, using Green Kubo formalism, diffusion coefficient for Ag NPs in IL and in the gas phase was calculated. We also calculated diffusion coefficients of anions and cations for pure IL and IL in the presence of different sizes of Ag NPs at different temperatures. The findings showed that the diffusion coefficient of anions and cations increases in proportion with temperature and the sizes of colloidal Ag NPs. Next, cationic transference number for pure IL and IL in the presence of Ag NPs, electrical conductivity of pure IL, and IL with different sizes of Ag NPs were calculated and compared. After that, the calculated diffusion coefficient and electrical conductiv...

The potential toxicity of engineered nanoparticles (NPs) for humans and the environment represents an emerging issue. Since the aquatic environment represents the ultimate sink for NP deposition, the development of suitable assays is needed to evaluate the potential impact of NPs on aquatic biota. The immune system is a sensitive target for NPs, and conservation of innate immunity represents an useful basis for studying common biological responses to NPs. Suspension-feeding invertebrates, such as bivalves, are particularly at risk to NP exposure, since they have extremely developed systems for uptake of nano and microscale particles integral to intracellular digestion and cellular immunity. Evaluation of the effects of NPs on functional parameters of bivalve immunocytes, the hemocytes, may help understanding the major toxic mechanisms and modes of actions that could be relevant for different NP types in aquatic organisms.In this work, a battery of assays was applied to the hemocytes of the marine bivalve Mytilus galloprovincialis to compare the in vitro effects of different n-oxides (n-TiO2, n-SiO2, n-ZnO, n-CeO2) chosen on the basis of their commercial and environmental relevance. Physico-chemical characterization of both primary particles and NP suspensions in artificial sea water-ASW was performed. Hemocyte lysosomal and mitochondrial parameters, oxyradical and nitric oxide production, phagocytic activity, as well as NP uptake, were evaluated. The results show that different n-oxides rapidly elicited differential responses hemocytes in relation to their chemical properties, concentration, behavior in sea water, and interactions with subcellular compartments. These represent the most extensive data so far available on the effects of NPs in the cells of aquatic organisms. The results indicate that Mytilus hemocytes can be utilized as a suitable model for screening the potential effects of NPs in the cells of aquatic invertebrates, and may provide a basis for future experimental work for designing environmentally safer nanomaterials.

Nitrogen heterocyclic carbenes (NHCs) are emerging as effective substitutes for conventional thiol ligands in surface functionalization of nanoparticles (NPs), offering exceptional stability to NPs under harsh conditions. However, the highly reactive feature of NHCs limits their use in introducing chemically active groups onto the NP surface. Herein, we develop a general yet robust strategy for the efficient surface functionalization of NPs with copolymer ligands bearing various functional groups. The polymer ligands consist of a multiple NHCs block, utilized for surface binding on NPs, alongside a poly(reactive ester) block intended for incorporating functional groups. The multiple NHCs block enables NPs with excellent colloidal stability across a broader range of pH values (0-14), temperature variations (-78 °C-100 °C), and electrolyte concentrations (0-1000 mM). Through the in situ ammonolysis of the poly(reactive ester) block, various active functional groups can be individually or together introduced on the NP surface. We further demonstrate the chemical reactivity of these functionalized NPs, including addition polymerization, Diels-Alder and Schiff base reactions. This method is applicable to various types of NPs, including metal NPs, metal oxide NPs, and even upconversion NPs, thereby paving new pathways for the design and creation of nanoparticle-based functional materials.

Investigation of the adsorption of size-selected Pt colloidal nanoparticles on high-surface-area graphene powders for methanol oxidation reaction

Luminescent lanthanide (Ln3+ = Pr, Nd, Sm, Eu, and Tb)-ions doped calcium molybdate(CaMoO4) nanoparticles(NPs) were prepared by the polyol wet-chemical route. X-ray diffraction (XRD) pattern of all samples showed the formation of a single-phase scheelite type tetragonal structure with an average crystalline size over 21.6-33.4nm. Thermal stability was evaluated to study the surface-anchored functional groups by weight loss measurement. Fourier transform infrared (FTIR) spectra were recorded to identify the adsorbed functional groups. Aqueous dispersibility and colloidal stability were recorded with the help of the UV/visible absorption spectra. These nanocrystals formed semi-transparent colloidal solutions after being evenly disseminated in aqueous media. The doping of the luminescent ions significantly affects the crystal structure and photoluminescence (PL) properties of the CaMoO4:Ln3+ NPs. In a comparative analysis of the absorption spectra, bandgap, Raman-active modes, and luminescent properties, they were greatly influenced by altering the dopant ion due to the variation in the atomic radius of the element. The doping of smaller atomic radius Ln3+-ions distorts the unit cell, and, subsequently, bond angle/length alters the symmetry of the host crystal. The distorted crystal lattice affects the crystalline, size, lattice parameter, band gap values, Raman active vibrational modes, and luminescent efficiency. The distorted crystal structure of the host lattices facilitates the movement of the oxygen vacancies through charge transfer, resulting in efficiently suppressed emission efficiency.Graphical abstract.

Polymer nanoparticles (NPs) can be highly attractive in numerous applications, including biomedicine, where the use of inorganic matter may be detrimental for living tissues. In conventional wet chemistry, polymerization and functionalization of NPs with specific chemical groups involves complex and often numerous reactions. Here, we report on a solvent-free, single-step, low-temperature plasma-based synthesis of carboxylated NPs produced by the polymerization of acrylic acid under the conditions of a glow discharge. In a monomer-deficient regime, the strong fragmentation of monomer molecules by electron impact results in the formation of 15 nm-sized NPs with <1% retention of the carboxyl groups. In an energy-deficient regime, larger 90 nm-sized NPs are formed with better retention of carboxyl groups that reaches 16%. All types of NPs exhibit a glass transition above room temperature, which makes them highly stable in an aqueous environment with no dissolution or swelling. The NPs are also found to degrade thermally when heated above 150 °C, with a decrease in the mean NP size but with retention of the chemical composition. Thus, plasma polymerization proves to be a versatile approach for the production of polymer NPs with a tunable size distribution, chemical composition, and physical properties.

This study evaluated the influence of metal oxide nanoparticles (NPs) (Ag2O, TiO2) and their mixture on activated sludge for 180 days. When tested, a mixture of NPs at 1 and 10 mg/L had greater impact than individual NPs, in which maximum reduction in chemical oxygen demand (COD) elimination (76.3%) was observed after 150 days for 1 mg/L (500 mg/L COD concentration) and after 180 days (70.2%) for 10 mg/L (250 mg/L COD concentration). TiO2 had higher inhibition on COD reduction than Ag2O NPs at 1 and 10 mg/L. An antagonistic effect was observed in which the combination of individual NPs had a greater effect than a mixture of NPs. Reduction in COD elimination was found to be dependent on NP type and concentration (p < 0.05). Further, metal ion concentration was higher in sludge than supernatant irrespective of NPs, while microscopic analysis showed the presence of NPs inside activated sludge. Among NPs tested, the concentration of Ti4+ ion was greater in sludge than in the Ag+ ion, thus indicating that TiO2 has a greater affinity than Ag2O NPs. All three factors (NP type, NP concentration, organic concentration) play a significant role in imparting COD removal (p < 0.05). Future studies are required to quantify NP concentration to minimize NP effect on plant performance.