Hydrophobic NPs Research Articles

Efficient Strategy to Synthesize Tunable pH-Responsive Hybrid Micelles Based on Iron Oxide and Gold Nanoparticles.

The preparation of multifunctional nanomaterials based on inorganic nanoparticles with organic materials has emerged as a promising strategy for the development of new nanomedicines for in vitro and in vivo biomedical applications. Here, we synthesized pH-responsive hybrid inorganic micelles by combining a novel pH-responsive amphiphilic molecule with hydrophobic payloads. This amphiphile was synthesized in a one-pot reaction and self-assembled readily into micelles under acidic pH conditions. In the presence of hydrophobic NP payloads such as AuNPs or IONPs, the amphiphile self-organized around them through hydrophobic interactions, resulting in the formation of colloidally stable hybrid micelles. The size of the hydrophobic NPs determined the pH-response of the inorganic hybrid micelles, which is tuned from pH 7 to 11 for our pH-responsive amphiphilic molecule. This achievement represents a novel approach for the synthesis of tunable pH-responsive hybrid micelles based on inorganic NPs for biomedical imaging, hyperthermia treatment, and also drug delivery nanosystems.

Driving Role of Zinc Oxide Nanoparticles with Different Sizes and Hydrophobicity in Metabolic Response and Eco-Corona Formation in Sprouts (Vigna radiata).

Zinc oxide nanoparticles (ZnO NPs) cause biotoxicity and pose a potential ecological threat; however, their effects on plant metabolism and eco-corona evolution between NPs and organisms remain unclear. This study clarified the molecular mechanisms underlying physiological and metabolic responses induced by three different ZnO NPs with different sizes and hydrophobicity in sprouts (Vigna radiata) and explored the critical regulation of eco-corona formation in root-nano systems. Results indicated that smaller-sized ZnO inhibited root elongation by up to 37.14% and triggered oxidative burst and apoptosis. Metabolomics confirmed that physiological maintenance after n-ZnO exposure was mainly attributed to the effective stabilization of nitrogen fixation and defense systems by biotransformation of the flavonoid pathway. Larger-sized or hydrophobic group-modified ZnO exhibited low toxicity in sprouts, with 0.89-fold upregulation of citrate in central carbon metabolism. This contributed to providing energy for resistance to NP stress through amino acid and carbon/nitrogen metabolism, accompanied by changes in membrane properties. Notably, smaller-sized and hydrophobic NPs intensely stimulated the release of root metabolites, forming corona complexes with exudates. The hydrogen-bonded wrapping mechanism in protein secondary structure and hydrophobic interactions of heterogeneous functional groups drove eco-corona formation, along with the corona evolution intensity of n-ZnO > s-ZnO > b-ZnO based on higher (α-helix + 3-turn helix)/β-sheet ratios. This study provides crucial insight into metabolic and eco-corona evolution in bionano fates.

Fabrication of Self-Healable, Robust, and Superhydrophobic Nanocomposite Films

Despite the recent advances in nature-inspired superhydrophobic surfaces with multifunctional properties such as self-healing, self-cleaning, antibacterial material, anti-biofouling, and oil-water separation in various industrial applications, there have been very few reports of robust superhydrophobic surfaces fabricated via a low-cost method. Herein, we report a rationally designed, self-healable, robust, and superhydrophobic nanocomposite film, fabricated by a one-step reaction process from a multi-component solution. These superhydrophobic nanocomposite films can be readily fabricated over a large area with high throughput via simple spray coating of the component solution. As the spray-coating materials, we used functionalized hydrophobic silica nanoparticles (hydrophobic-SiO2 NPs) to achieve hierarchical textured structures, and low surface energy. Then, thermal crosslinkers and long hydrocarbon silanes were added to improve the stability and hydrophobicity of the fabricated nanocomposite films. Because of the synergetic effect of the hydrophobic NPs and crosslinked polymeric compounds, the spray-coated superhydrophobic nanocomposite films exhibited excellent superhydrophobicity (static water contact angles > 150°), high transparency (>80%), high stability, and self-healing abilities. Tests confirmed the rationally designed, solution-based spray coating method provides a simple route to construct transparent, robust, and self-healing superhydrophobic surfaces, with high throughput and large area, which can be utilized in various industrial applications, including conventional products and advanced non-wetting surfaces.

Silver nanoparticles synthesis and their effect on the SOPC lipid structure

We focus our attention on the influence of hydrophobic silver nanoparticles (Ag NPs) on the 1-Stearoyl-2-oleoylsn-glycero-3-phosphocholine (SOPC) model system. Results obtained by differential scanning calorimetry (DSC) and infrared (IR) spectroscopy were compared to their counterpart for lipid systems with incorporated hydrophobic gold nanoparticles (AuNPs) and pure SOPC lipid in a water environment. The results show a strong effect of hindering the gel-to-liquid crystalline phase transition for both types of noble metal hydrophobic NPs. The effect of the phase transitions shift to the lower temperatures is more pronounced for the silver particles for the concentrations studied. According to the IR spectral analyses, no negative effect is observed of the NPs on the lipid hydration for the concentration studied, and the plasmon effect of the Ag NPs appears to be more pronounced.

A non-classical route of efficient plant uptake verified with fluorescent nanoparticles and root adhesion forces investigated using AFM

Classical plant uptake is limited to hydrophilic or water-dispersible material. Therefore, in order to test the uptake behaviour of hydrophobic particles, here, we tested the fate of hydrophobic particles (oleylamine coated Cu2-xSe NPs (CS@OA)) in comparison to hydrophilic particles (chitosan-coated Cu2-xSe NPs (CS@CH)) by treatment on the plant roots. Surprisingly, hydrophobic CS@OA NPs have been found to be ~ 1.3 times more efficient than hydrophilic CS@CH NPs in tomato plant root penetration. An atomic force microscopy (AFM) adhesion force experiment confirms that hydrophobic NPs experience non-spontaneous yet energetically favorable root trapping and penetration. Further, a relative difference in the hydrophobic vs. hydrophilic NPs movement from roots to shoots has been observed and found related to the change in protein corona as identified by two dimensional-polyacrylamide gel electrophoresis (2D-PAGE) analysis. Finally, the toxicity assays at the give concentration showed that Cu2-xSe NPs lead to non-significant toxicity as compared to control. This technology may find an advantage in fertilizer application.

Tuning the Surface Chemistry of Melanin-Mimetic Polydopamine Nanoparticles Drastically Enhances Their Accumulation into Excised Human Skin.

Melanin-mimetic polydopamine nanoparticles (PDA NPs) are emerging as promising candidates for topical and transdermal drug delivery because they mimic melanin, a naturally occurring skin pigment. However, our knowledge of their interactions with human skin remains limited. Hence, we set out to investigate the role of PDA NP surface chemistry in modulating their skin deposition. PDA NPs were synthesized by base-catalyzed oxidative self-polymerization of dopamine and functionalized with poly(ethylene glycol) (PEG) bearing different termini to obtain neutral, anionic, cationic, and hydrophobic PEGylated NPs. NPs were characterized by dynamic light scattering, transmission electron microscopy, Fourier transform-infrared spectroscopy, and X-ray photoelectron spectroscopy. The NPs were then labeled with rhodamine B, and their skin interactions were investigated both in vitro, using a Strat-M membrane, and ex vivo, using excised whole thickness human skin. In vitro diffusion studies revealed that the NPs did not permeate transdermally, rather the NPs accumulated in the Strat-M membrane after 24 h of incubation. Membrane deposition of the NPs showed a strong dependence on surface chemistry, with anionic (unmodified and carboxyl-terminated PEGylated) NPs achieving the highest accumulation, followed by neutral and cationic NPs, whereas hydrophobic NPs achieved the lowest degree of accumulation. In ex vivo permeation studies, we observed that surface modification of PDA NPs with PEG serving as an antifouling coating is essential to maintaining colloidal stability upon skin contact. Moreover, anionic PEGylated NPs were able to achieve 78% skin accumulation, which was significantly higher than neutral and cationic NPs (51 and 34% accumulation, respectively). Our findings provide important insights into the role of surface chemistry in enhancing the skin accumulation of melanin-mimetic PDA NPs as potential sunscreens and carriers for skin-targeted treatments.

Rapid evaluation of gold nanoparticle-lipid membrane interactions using a lipid/polydiacetylene vesicle sensor.

Surface modification of gold nanoparticles (AuNPs) has significant and complicated effects on their interactions with cell membranes. In this study, we used a lipid/polyacetylene (PDA) vesicle sensor as the lipid membrane model to evaluate AuNP-lipid membrane interactions. Based on the colorimetric response (CR) of PDA vesicles before and after incubation with AuNPs, it was found that the interaction was highly dependent on the surface charge of AuNPs. As compared to the positively charged NPs, neutral and zwitterionic NPs adsorbed much less on the lipid membrane. Negatively charged NPs did not induce any noticeable color changes even at high concentrations. A class of cationic AuNPs with different degrees of surface hydrophobicity was further selected to investigate the role of hydrophobicity in interacting with lipid/PDA vesicles, and log(EC50) was employed as the evaluation index. According to the log(EC50)-NP concentration curve, the hydrophobicity of NPs enhanced the lipid membrane affinity, but electrostatic interactions weakened this effect. Finally, different concentrations of bovine serum albumin (BSA) were used to study the effect of the protein corona on NP-lipid membrane interactions. The formation of a NP-protein corona was found to mask the electrostatic interactions, leading to the decrease of the CR values of cationic NPs, and highly hydrophobic NPs were less affected by a low concentration of BSA due to the strong hydrophobic interactions. Although the effect of NP surface properties on their interactions with cells is far more complicated, our study provides a rapid and effective method for the evaluation of the interactions between surface modified AuNPs and lipid membranes.

Predominant Factor Determining Thermal Conductivity Behavior of Nanofluid: Effect of Cluster Structures with Various Nanoparticles

Despite several research efforts, the detailed mechanism that dominates the thermal conductivity of nanofluids has not been explained. We investigated the effect of the chemical surface design of NPs (hydrophobic–hydrophilic balance of the NPs containing Janus surface) and verified the influence of their self–assembled structures on the thermal conductivity of a nanofluid using molecular simulation. When hydrophobic (HO) NPs are added to a nanofluid, they only form one large cluster because they do not prefer to be in contact with water molecules. Hence, an increment in the thermal conductivity of the nanofluid added with HO NPs was observed. On the contrary, the mean cluster size of Janus NPs was limited because of their limited HO superficial areas (attractive domains). Hence, an increment in the enhancement ratio of thermal conductivity was not observed even when the volume fraction of the NPs (ϕNP) was increased. Thus, our results demonstrate that the mean cluster size of NPs is the key factor for thermal conductivity enhancement. In addition, this study reveals that it is possible to control the thermal conductivity of nanofluids (or the mean cluster size of Janus NPs) using Janus NPs with surfaces designed using anisotropic chemical interactions.

Synergic effects of hydrophilic and hydrophobic nanoparticles on performance of nanocomposite distillation membranes: An experimental and numerical study

Abstract Supported flat sheet nanocomposite polyvinylidenefluoride (PVDF) membranes embedded with hydrophilic TiO2, hydrophobic TiO2, or the combination of them were fabricated via phase inversion process. The membranes were characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, atomic force spectroscopy, and the measurement of water contact angle and liquid entry pressure of water and subjected to tests on vacuum membrane distillation (VMD) performance. Addition of appropriate amounts of either hydrophilic or hydrophobic NPs was found to enhance VMD flux but hydrophilic NPs caused significant decrease of liquid entrance pressure of water (LEPw) while hydrophobic particles did not show significant impacts on LEPw. Addition of both hydrophilic and hydrophobic NPs demonstrated synergistic effects in terms of both enhanced flux and LEPw due to their different but complimentary effects on membrane structures. At feed temperature of 27.5 °C, the VMD pure water permeate flux of the composite membrane embedded with 5 wt% hydrophilic TiO2 NPs and 2 wt% of hydrophobic TiO2 NPs (total 7 wt% NPs) was 4.26 kg/m2h with a LEPw of 28 psi, while those of neat PVDF membrane, the membrane embedded with 7 wt% of hydrophilic NP, and the membrane with 7 wt% hydrophobic nanoparticles were 0.335, 3.57, and 1.25 kg/m2 h, respectively, and the LEPw of these membranes were 51, 24 and 47 psi, respectively. It is noted that at 5 wt% addition, the flux of M-L5 (hydrophilic NPs) is 3 times higher than the M-B5 (hydrophobic NPs). Furthermore, by adding another 2 wt% of NPs, flux increment by M-L5-B2 (hydrophobic NPs) is 3.5 times higher than M-L7 (hydrophilic NPs). Therefore, in both the effects combined, the highest flux was achieved by M-L5-B2 indicating synergistic effect of hydrophilic and hydrophobic NPs on the membrane flux. The salt rejection of above 99% could be maintained for 3 h by the membrane in which both hydrophilic and hydrophobic NPs were loaded. Numerical analyses of heat and mass transfer were also carried out to study the impact of hydrophilic and hydrophobic NPs on membrane characteristics.

Interaction Between Hydrophobic Au Nanoparticles and Pulmonary Surfactant (DPPC) Monolayers.

Hydrophobic nanoparticles from the air get into the lungs through inhalation and firstly interact with pulmonary surfactant, which is essential for normal lung function. 1,2-dipalmitoyl-sn-glycerol-3-phosphocholine (DPPC) is the major component of pulmonary surfactant. Interaction between Langmuir monolayer of DPPC and hydrophobic Au nanoparticles (Au NPs) were investigated in this study by atomic force microscope. The experimental results indicated that incorporation of hydrophobic Au NPs into the monolayer hindered the phase transition, reduced the compressibility of monolayer and disrupted the large micro-domains in liquid-condensed (LC) phase into smaller ones. Moreover, Au NPs that modulated by DPPC domains formed wandering wires, which were enclosed LC phase domains, at low concentration and relatively large islands at high concentration. The large islands still remained on the water surface after five cycles of compression-expansion at high concentration of Au NPs, but single NPs or wires with 1-2 particle width escaped into the water during the compression through the help of DPPC coating. The interaction between hydrophobic NPs and pulmonary surfactant provides an insight into the toxicological effects of inhaled NPs from the atmosphere to the function of pulmonary surfactant in the lung.

Impact of coated TiO2-nanoparticles used in sunscreens on two representative strains of the human microbiota: Effect of the particle surface nature and aging

The impact of two differently coated TiO2-nanoparticles (NPs) was evaluated on two representative bacteria from the cutaneous microbiota (Staphylococcus aureus and Pseudomonas fluorescens) in conditions of use. Particles were coated in order to exhibit either hydrophilic or hydrophobic behavior. A first exposure scenario within some fresh/aged model emulsions was developed in order to measure both the impact of the NPs presence and their surface nature during the emulsions conservation. Thanks to this protocol, it was demonstrated that, during aging, the hydrophobic NPs modified the physicochemical characteristics of the emulsions, such as the pH or the colloids sizes, and favored the development of potential pathogenic bacteria. A second scenario was then envisaged, aiming to mimic the exposition of the skin, especially of the cutaneous bacteria, to NPs. Tested NPs were extracted from emulsions with different aging, and results highlighted the importance of both the NP coating nature and their history in emulsion. The different NPs impacts on the bacteria growth were discussed and linked to their surface properties modifications during aging, as polarity and charges. Finally, through two exposition scenarios, this work highlights the major impact of the NPs surface properties on bacteria.

Determination of parabens in waters by magnetically confined hydrophobic nanoparticle microextraction coupled to gas chromatography/mass spectrometry

In this article, magnetically confined hydrophobic nanoparticle microextraction is applied for the analysis of parabens in water samples by gas chromatography (GC)–mass spectrometry (MS). The hydrophobic magnetic nanoparticles (MNPs) are confined in a device by means of a mini-magnet which also allows the stirring of the unit. A thin layer of MNPs, which presents an optimal surface to volume ratio, is the responsible of the analytes extraction. Although the superficial area of the layer is lower than the potential one obtained with a perfect dispersion of the MNPs, the latter approach is hard to be performed with highly hydrophobic MNPs and therefore the proposed configuration is more useful from a practical point of view. This fact, together with the inherent stirring of the unit, enhances the kinetic extraction and therefore the sensitivity of the procedure compared to conventional dispersion conditions. The most influential extraction parameters were evaluated, including the pH and ionic strength of the sample, the stirring rate, the extraction time, the amounts of MNPs, the volume of sample and the elution conditions. Under the most favorable extraction parameters, the method showed good linearity, repeatability (relative standard deviation below 7.1%, n = 7) and sensitivity in the ng per liter range. The proposed method was demonstrated to be a simple, fast and efficient method for the analysis of parabens in sea and swimming pool water samples. • Magnetically confined hydrophobic NPs microextraction is coupled to GC/MS. • This combination is applied to the determination of parabens in waters. • Their presence in sea and swimming pool waters has been detected. • The limits of detection were acceptable with good precision and recoveries.

Integration of Gold Nanoparticles into Bilayer Structures via Adaptive Surface Chemistry

We describe the spontaneous incorporation of amphiphilic gold nanoparticles (Au NPs) into the walls of surfactant vesicles. Au NPs were functionalized with mixed monolayers of hydrophilic (deprotonated mercaptoundecanoic acid, MUA) and hydrophobic (octadecanethiol, ODT) ligands, which are known to redistribute dynamically on the NP surface in response to changes in the local environment. When Au NPs are mixed with preformed surfactant vesicles, the hydrophobic ODT ligands on the NP surface interact favorably with the hydrophobic core of the bilayer structure and guide the incorporation of NPs into the vesicle walls. Unlike previous strategies based on small hydrophobic NPs, the present approach allows for the incorporation of water-soluble particles even when the size of the particles greatly exceeds the bilayer thickness. The strategy described here based on inorganic NPs functionalized with two labile ligands should in principle be applicable to other nanoparticle materials and bilayer structures.

Transparent, Superhydrophobic Surfaces from One-Step Spin Coating of Hydrophobic Nanoparticles

We study the nonwettability and transparency from the assembly of fluorosilane modified silica nanoparticles (F-SiO(2) NPs) via one-step spin-coating and dip-coating without any surface postpassivation steps. When spin-coating the hydrophobic NPs (100 nm in diameter) at a concentration ≥ 0.8 wt % in a fluorinated solvent, the surface exhibited superhydrophobicity with an advancing water contact angle greater than 150° and a water droplet (5 μL) roll-off angle less than 5°. In comparison, superhydrophobicity was not achieved by dip-coating the same hydrophobic NPs. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) images revealed that NPs formed a nearly close-packed assembly in the superhydrophobic films, which effectively minimized the exposure of the underlying substrate while offering sufficiently trapped air pockets. In the dip-coated films, however, the surface coverage was rather random and incomplete. Therefore, the underlying substrate was exposed and water was able to impregnate between the NPs, leading to smaller water contact angle and larger water contact angle hysteresis. The spin-coated superhydrophobic film was also highly transparent with greater than 95% transmittance in the visible region. Further, we demonstrated that the one-step coating strategy could be extended to different polymeric substrates, including poly(methyl methacrylate) and polyester fabrics, to achieve superhydrophobicity.

Experimental evidence for predicted transmembrane peptide topography: Incorporation of hydrophobic peptide α‐helical rods with an N‐terminal positive charge having a length comparable to the thickness of lipid bilayers into the membranes

Liposomes consisting of egg yolk phosphatidylcholine and hydrophobic peptides Nps- and Cl-.+H2-(Met-Met-Leu)n-OEt (n = 6-10) with various polypeptide chain lengths were prepared by the sonication method. The conformation of the peptides incorporated into the liposomes was examined by CD spectroscopy. All the peptides incorporated assumed alpha-helical conformation. Quantitative analyses of the peptides and lipids in the membranes showed that the concentration of the peptides with a positive charge at the N-terminus in the liposomes decreased markedly as the peptide chain length increased, reaching zero for the peptides over n = 8. The peptides without a positive charge were hardly incorporated into the liposomes. Infrared attenuated reflection spectroscopy of multilayered membranes containing the peptides suggests that the axis of the alpha-helical peptide rods is oriented in parallel with the molecular axis of lipids in the membranes. These results suggest that the hydrophobic peptides can be incorporated into the lipid bilayers of the liposomes in the alpha-helical conformation, the rods of which have a length comparable to the thickness of the lipid bilayers, and the N-terminal positive charge of the peptides is essential for the stable peptide incorporated into the membranes.