Nanoscale Droplets Research Articles

Molecular dynamics study of water vapor condensation on a composite wedge-shaped surface with multi wettability gradients

To find out whether the composite wedge-shaped surface with multi wettability gradients could accelerate the condensate drainage in a micro view, the model of water vapor condensation on such surface was built and studied by molecular dynamics (MD). The vertex angle and wettability gradient of wedge-shaped surface were investigated to obtain the best condition for accelerated removal of condensate. The wettability gradient of two surfaces was divided into three groups: Group A (hydrophilic - super hydrophilic), Group B (hydrophobic - hydrophilic) and Group C (hydrophobic - super hydrophobic). The vertex angle was changed from 7°, 10°, 14° to 20°. Filmwise condensation (FWC) appeared in Group A and dropwise condensation (DWC) formed in Group B. However, there was no condensation in Group C. Although the FWC in Group A could drain, the drainage rate was slow. Only in Group B, the DWC could form water droplet and the movement of droplet could be controlled by the wedge-shaped surface, which was helpful for condensate drainage. When comparing the effect of different vertex angle, the smaller vertex angle could finish the FWC more quickly in Group A due to the smaller area of the super hydrophilic surface. In group B, small wedge-shaped surface would take more time to form main nuclei, while large wedge-shaped surface forming two nuclei also took more time to form a whole nanoscale droplet. In that case, DWC rate was quicker and condensation drainage was better in vertex angle of 14° in these four conditions.

Thermal fluctuations drive nanoscale droplet formation

Thermal fluctuations drive nanoscale droplet formation

Theoretical modeling and analysis of material removal characteristics for KDP crystal in abrasive-free jet processing.

Traditional KDP polishing methods, such as magnetorheological finishing (MRF), ion-beam figuring (IBF), and chemical mechanical polishing (CMP), are limited by either hard-to-remove residual particles, unavoidable heating effect, or applicability that is restricted to large-sized KDP. The abrasive-free jet polishing (AFJP) is regarded as a promising polishing method that can circumvent the above issues. KDP AFJP makes use of a thermodynamically and kinetically stable ionic liquid (IL) microemulsion that contains nanometer range water droplets evenly dispersed in the non-aqueous carrier liquid. The sprayed out nanoscale water droplets can remove material through dissolution. In this paper, the normal impinging of a nanoscale water droplet on the KDP surface is investigated. And then a materials removal model is proposed for water droplets. This model considers two major modes, namely deformation of a water droplet in compressing and deformation restoring of a water droplet in slipping process. Finally, KDP AFJP spot experiments were then conducted to validate the model veracity. The proposed model fits well with the simulation and experimental results which further suggest KDP AFJP's feasibility. This proposed model provides a good explanation for KDP AFJP's removal mechanism.

Electrospray Functionalization of Titanium Dioxide Nanoparticles with Transferrin for Cerenkov Radiation Induced Cancer Therapy.

Titanium dioxide (TiO2) nanoparticles have shown success as photosensitizers in the form of light-based cancer therapy called Cerenkov radiation induced therapy (CRIT). While TiO2 nanoparticles have been reported to be an effective therapeutic agent, there has been little work to control their functionalization and stability in aqueous suspension. In this work, the controlled coating of 25 nm diameter TiO2 nanoparticles with the glycoprotein transferrin (Tf) for application in CRIT was demonstrated using an electrospray system. Monodisperse nanoscale droplets containing TiO2 and Tf were dried during flight, coating the proteins on the surface of the metal oxide nanoparticles. Real-time scanning mobility particle sizing, dynamic light scattering, and transmission electron microscopy show efficient control of the Tf coating thickness when varying the droplet size and the ratio of Tf to TiO2 in the electrospray precursor suspension. Further, the functionality of Tf-coated TiO2 nanoparticles was demonstrated, and these particles were found to have enhanced targeting activity of Tf to the Tf receptor after electrospray processing. The electrospray-coated Tf/TiO2 particles were also found to be more effective at killing the multiple myeloma cell line MM1.S than that of nanoparticles prepared by other reported functionalization methods. In summary, this investigation not only provides a single-step functionalization technique for nanomaterials used in Cerenkov radiation induced therapy but also elucidates an electrospray coating technique for nanomaterials that can be used for a wide range of drug design and delivery purposes.

Solvent Exchange in a Hele–Shaw Cell: Universality of Surface Nanodroplet Nucleation

Solvent exchange (also called solvent shifting or Ouzo effect) is a generally used bottom-up process to mass-produce nanoscale droplets. In this process, a good solvent for some oil is displaced by a poor one, leading to oil nanodroplet nucleation and subsequent growth. Here we perform this process on a hydrophobic substrate so that sessile droplets so-called surface nanodroplets-develop, following the work of Zhang et al. [Zhang, X.; Lu, Z.; Tan, H.; Bao, L.; He, Y.; Sun, C.; Lohse, D. Proc. Natl. Acad. Sci. U.S.A. 2015, 122, 9253-9257]. In contrast to what was done in that paper, we chose a very well-controlled Hele-Shaw geometry with negligible gravitational effects, injecting the poor solvent in the center of the Hele-Shaw cell, and characterize the emerging nanodroplets as a function of radial distance and flow rates. We find that the mean droplet volume per area <Vol>_area strongly depends on the local Peclet number Pe and follows a universal scaling law <Vol>_area~Pe^(3/4). Moreover, the probability distribution function of the droplet volume strongly depends on the local Pe as well, regardless of the flow rates and radial distance, giving strong support to the theoretical model of the solvent exchange process developed in Zhang et al.'s work.

Perfluorocarbon nanodroplets can reoxygenate hypoxic tumors in vivo without carbogen breathing.

Nanoscale perfluorocarbon (PFC) droplets have enormous potential as clinical theranostic agents. They are biocompatible and are currently used in vivo as contrast agents for a variety of medical imaging modalities, including ultrasound, computed tomography, photoacoustic and 19F-magnetic resonance imaging. PFC nanodroplets can also carry molecular and nanoparticulate drugs and be activated in situ by ultrasound or light for targeted therapy. Recently, there has been renewed interest in using PFC nanodroplets for hypoxic tumor reoxygenation towards radiosensitization based on the high oxygen solubility of PFCs. Previous studies showed that tumor oxygenation using PFC agents only occurs in combination with enhanced oxygen breathing. However, recent studies suggest that PFC agents that accumulate in solid tumors can contribute to radiosensitization, presumably due to tumor reoxygenation without enhanced oxygen breathing. In this study, we quantify the impact of oxygenation due to PFC nanodroplet accumulation in tumors alone in comparison with other reoxygenation methodologies, in particular, carbogen breathing.Methods: Lipid-stabilized, PFC (i.e., perfluorooctyl bromide, CF3(CF2)7Br, PFOB) nanoscale droplets were synthesized and evaluated in xenograft prostate (DU145) tumors in male mice. Biodistribution assessment of the nanodroplets was achieved using a fluorescent lipophilic indocarbocyanine dye label (i.e., DiI dye) on the lipid shell in combination with fluorescence imaging in mice (n≥3 per group). Hypoxia reduction in tumors was measured using PET imaging and a known hypoxia radiotracer, [18F]FAZA (n≥ 3 per group).Results: Lipid-stabilized nanoscale PFOB emulsions (mean diameter of ~250 nm), accumulated in the xenograft prostate tumors in mice 24 hours post-injection. In vivo PET imaging with [18F]FAZA showed that the accumulation of the PFOB nanodroplets in the tumor tissues alone significantly reduced tumor hypoxia, without enhanced oxygen (i.e., carbogen) breathing. This reoxygenation effect was found to be comparable with carbogen breathing alone.Conclusion: Accumulation of nanoscale PFOB agents in solid tumors alone successfully reoxygenated hypoxic tumors to levels comparable with carbogen breathing alone, an established tumor oxygenation method. This study confirms that PFC agents can be used to reoxygenate hypoxic tumors in addition to their current applications as multifunctional theranostic agents.

Chromium 10× Single-Cell 3' mRNA Sequencing of Tumor-Infiltrating Lymphocytes.

Chromium 10× 3' V2 protocol is a 3' end counting single-cell mRNA sequencing protocol that allows to process and sequence RNA from thousands of cells in parallel. Chromium10× by 10× Genomics is an emulsion-based device that enables to compartmentalize single cells along with sets of uniquely barcoded primers and reverse transcription reagents into nanoscale droplets that are used as reaction chambers to generate barcoded full-length cDNA from single cells. After RT reaction single-stranded barcoded cDNAs are pooled together and processed to generate sequencing libraries compatible with the standard Illumina platforms. Here we show in detail the main steps of the protocol applied to the analysis of tumor-infiltrating T lymphocytes (TILs). The main steps are cell preparation, cDNA synthesis, library construction, and sequencing.This protocol refers specifically to the CG00052_SingleCell3_ReagentKitv2UserGuide_RevD downloadable from 10× Genomics website ( https://www.10xgenomics.com ) and does not substitute it. Always refer to this guide, paying attention to updates and revisions.

Novel tunable super-tough materials from biodegradable polymer blends: nano-structuring through reactive extrusion.

Structuring blends on sub-micrometer scales, especially nano-scales, has a higher potential for improving their thermomechanical properties. Here, we propose a design strategy to fabricate compatible nano-blends by manipulating the reactions between two biodegradable polymers, e.g. polybutylene succinate (PBS) and polybutylene adipate terephthalate (PBAT), with extremely low free radical contents through reactive extrusion processing. Observed by transmission electron microscopy (TEM) and atomic force microscopy (AFM), it is found that PBAT is tightly surrounded by large amounts of PBS–PBAT co-polymers and dispersed in a PBS matrix with a particle size of less than 100 nm. We show how impact strength and polymer moduli can be improved simultaneously by decreasing the small amount of dispersed phase into nano-scale (droplet or lamina structures). With 5 wt% PBAT content in the PBS–PBAT blend, the notched impact strength of PBS is increased 1200% and the Young's modulus is increased 15%. Through in situ rheological monitoring and Fourier-transform infrared spectroscopy (FTIR) studies, the reason why nano-blends can be formed in such a low amount of peroxide is illustrated. Our investigation most significantly indicates the transformation of the partially compatible PBS–PBAT micro-blend into a fully compatible PBS–PBAT through nano-structuring. This work addresses the importance of reaction rate and mechanism in favoring the formation of co-polymers rather than homo-polymer crosslinking or self-decomposition in polymer blend modification via reactive extrusion design.

Controlling nanoemulsion surface chemistry with poly(2-oxazoline) amphiphiles.

Emulsions are dynamic materials that have been extensively employed within pharmaceutical, food and cosmetic industries. However, their use beyond conventional applications has been hindered by difficulties in surface functionalization, and an inability to selectively control physicochemical properties. Here, we employ custom poly(2-oxazoline) block copolymers to overcome these limitations. We demonstrate that poly(2-oxazoline) copolymers can effectively stabilize nanoscale droplets of hydrocarbon and perfluorocarbon in water. The controlled living polymerization of poly(2-oxazoline)s allows for the incorporation of chemical handles into the surfactants such that covalent modification of the emulsion surface can be performed. Through post-emulsion modification of these new surfactants, we are able to access nanoemulsions with modified surface chemistries, yet consistent sizes. By decoupling size and surface charge, we explore structure-activity relationships involving the cellular uptake of nanoemulsions in both macrophage and non-macrophage cell lines. We conclude that the cellular uptake and cytotoxicity of poly(2-oxazoline)-stabilized droplets can be systematically tuned via chemical modification of emulsion surfaces.

Effect of Ga droplet deposition rate on morphology of concentric quantum double rings

For the fabrication of particular nanostructures, Stranski-Krastanov (SK) growth mode driven by strain is most widely used. Meanwhile, another technique that is used to form the complex nanostructures is the droplet epitaxy technique, which is based on the deposition of group III element nanoscale droplets onto substrate and followed by the reaction with group V element for crystallization into III-V compound nanostructures. Droplet epitaxy technique is simple and flexible, and it does not require additional complicated processing and has potential to develop various quantum nanostructures. It, unlike standard MBE growth, exploits the sequential supply of group-III and group-V elements to form quantum nanostructures. Quantum rings are a special class of quantum-confinement structure that can be fabricated by the droplet epitaxy technique and have attracted wide attention due to the Aharonov-Bohm effect, which is specific to the topology of a ring. In this paper, GaAs/GaAs (001) concentric quantum double rings (CQDRs) are prepared by droplet epitaxy technique at different Ga droplet deposition rates in monolayer per second (ML/S). The 2 μm × 2 μm atomic force microscope images are obtained to show the morphologies of CQDRs. We study the effects of Ga droplet deposition rates (0.09 ML/s, 0.154 ML/s, 0.25 ML/s, 0.43 ML/s) on CQDRs. The results show that with the increase of Ga droplet deposition rate, the density of CQDRs increases and the radius of inner ring and the radius of outer ring decrease. According to the nucleation theory, through the relationship between the maximum cluster density and the Ga droplet deposition rate, the critical number of atom nucleations is found to be 5, which suggests that the stable Ga atom crystal nucleus should contain at least 5 Ga atoms in the process of forming Ga droplet, and a nucleation state transformation diagram is drawn in order to obtain an insight into the process of forming Ga droplet according to the nucleation theory and fitting results. The research results could be instructive for preparing the GaAs concentric quantum double rings that the density can be controlled by droplet epitaxy.

Hydrophobin-stabilized nanoemulsion produced by a low-energy emulsification process: A promising carrier for nutraceuticals

Hydrophobin II (HFBII) is an amphiphilic biopolymer that could be explored to stabilize oil-in-water nanoemulsions as nutraceutical delivery systems. This study reports the production of HFBII-stabilized nanoemulsions by a spontaneous emulsification process using copaiba oil as a bioactive lipid. HFBII was isolated from a wild-type Trichoderma reesei and characterized. A 23 full factorial design with three central points was used to obtain an optimal nanoemulsion system, whose physical-chemical properties were studied under different ionic strength and pH. The peptide similarity search allowed the identification of a series of 6 ion fragments from the isolated fraction, which can be attributed to the amino acid sequences of the HFBII database. The optimal nanoemulsion system presented a nanoscale droplet size (<200 nm), a narrow size distribution (PDI <0.2) and a negative zeta potential of ≈ −30 mV, which was stable at low salt content and pH values close to the neutrality. These results demonstrated the feasibility of using HFBII as a biopolymer to stabilize nanoemulsion systems. Furthermore, the HFBII-stabilized nanoemulsion is a promising carrier for nutraceuticals in food technology applications.

Nanoscale Morphology, Interfacial Hydrogen Bonding, Confined Crystallization and Greatly Improved Toughness of Polyamide 12/Polyketone Blends.

Nanostructured polyamide 12(PA12)/polyketone (PK) blends were fabricated by melt compounding. The nanoscale droplet and domain-in-domain morphologies depending on PK content were observed. When the content of PK was 10 vol %, the impact strength of the blend jumped from 6.8 to 111.9 kJ/m2 and further improved with an increasing content of PK. The toughening mechanism was found to be closely related with the morphology change from nanoscale droplet morphology to domain-in-domain morphology owing to the strong interfacial hydrogen bonding. The nanoscale morphology confinement and interfacial hydrogen bonding enhances the crystallization kinetics, while it lowers down the thermodynamic stability of the crystals. The toughening mechanisms were discussed based on these factors.

Nanodroplet Hydrodynamic Transformation of Uniform Amorphous Bilayer into Highly Modulated Ge/Si Island-Chains.

Geometric and compositional modulations are the principal parameters of control to tailor the band profile in germanium/silicon (Ge/Si) heteronanowires (NWs). This has been achieved mainly by alternating the feeding precursors during a uniaxial growth of Ge/Si NWs. In this work, a self-automated growth of Ge/Si hetero island-chain nanowires (hiNWs), consisting of wider c-Ge islands connected by thinner c-Si chains, has been accomplished via an indium (In) droplet-mediated transformation of uniform amorphous a-Si/a-Ge bilayer thin films. The surface-running In droplet enforces a circulative hydrodynamics in the nanoscale droplet, which can modulate the absorption depth into the amorphous bilayer and enable a single-run growth of a superlattice-like hiNWs without the need for any external manipulation. Meanwhile, the separation and accumulation of electrons and holes in the phase-modulated Ge/Si superlattice leads to a modulated surface potential profile that can be directly resolved by Kelvin probe force microscopy. This simple self-assembly growth and modulation dynamics can help to establish a powerful new concept or strategy to tailor and program the geometric and compositional profiles of more complex hetero nanowire structures, as promising building blocks to develop advanced nanoelectronics or optoelectronics.

Comparison of natural and synthetic surfactants at forming and stabilizing nanoemulsions: Tea saponin, Quillaja saponin, and Tween 80

HypothesisThis study compared the interfacial and emulsification properties of tea saponins, quillaja saponins, and Tween 80. We hypothesized that tea saponins are an effective and sustainable source of plant-based emulsifiers that could replace synthetic or animal-based emulsifiers in many commercial applications. ExperimentsInterfacial tension measurements were used to characterize the behavior of the three surfactants at an oil-water interface. The emulsifying properties of the surfactants were determined by preparing oil-in-water emulsions containing 10 wt% medium chain triglycerides (MCT) and varying surfactant levels (0.1–2 wt%) using high-pressure homogenization (pH 7). The impact of surfactant type on emulsion formation and stability was determined by measuring particle size, zeta–potential, microstructure, and creaming stability. FindingsThe tea saponins were capable of producing nano-scale droplets (d32 < 200 nm) at low surfactant-to-oil ratios (SOR < 0.1). Emulsions containing tea saponins remained stable to droplet aggregation when exposed to various temperatures (30–90 °C), salt levels (0–200 mM NaCl), and pH values (3–9). However, droplet flocculation and/or coalescence occurred under highly acidic (pH 2) and high ionic strength (300–500 mM NaCl) conditions. Tea saponin-coated oil droplets appeared to be mainly stabilized by a combination of electrostatic and steric repulsion. The tea saponins behaved similarly or better than the other two emulsifiers under most conditions. These results suggest that tea saponins are effective plant-based surfactants that may have applications in commercial products.

Generalized line tension of water nanodroplets

We compare all-atom simulations of nanoscale water droplets of spherical and cylindrical morphologies on flat surfaces with tunable polarities. We find that for both morphologies, the contact angle depends, albeit differently, on the droplet size, which can be well described by the modified Young equation with an apparent line tension as a fitting parameter. In order to quantify the origin of the apparent line tension, we invoke a continuum-level description of the droplets for both morphologies. This enables us to decompose the apparent line tension into individual components that stem from a contact-angle dependent line tension and the Tolman correction to the surface tension.

Enhancement of Coalescence-Induced Nanodroplet Jumping on Superhydrophobic Surfaces.

Coalescence-induced droplet self-jumping on superhydrophobic surfaces has received extensive attentions over the past decade because of its potential applications ranging from anti-icing materials to self-sustained condensers, in which a higher jumping velocity vj is always expected and favorable. However, the previous studies have shown that there is a velocity limit with vj ≤ 0.23 uic for microscale droplets and vj ≤ 0.127 uic for nanoscale droplets, where uic is referred to as the inertial-capillary velocity. Here, we show that the jumping velocity can be significantly increased by patterning a single groove, ridge, or more hydrophobic strip, whose size is comparable with the radius of coalescing droplets, on a superhydrophobic surface. We implement molecular dynamics simulations to investigate the coalescence of two equally sized nanodroplets (8.0 nm in radius) on these surfaces. We found that a maximum vj = 0.23 uic is achieved on the surface with a 1.6 nm high and 5.9 nm wide ridge, which is 1.81 times higher than the nanoscale velocity limit. We also demonstrate that the presence of groove, ridge, and strip alters coalescence dynamics of droplets, leading to a significantly shortened coalescence time which remarkably reduces viscous dissipation during coalescence; thus, we believe that the present approach is also effective for microscale droplet jumping.

Dynamics of Nanodroplets on Vibrating Surfaces.

We report the results of molecular dynamics investigations into the behavior of nanoscale water droplets on surfaces subjected to cyclic-frequency normal vibration. Our results show, for the first time, a range of vibration-induced phenomena, including the existence of the following different regimes: evaporation, droplet oscillation, and droplet lift-off. We also describe the effect of different surface wettabilities on evaporation. The outcomes of this work can be utilized in the design of future nanoengineered technologies that employ surface/bulk acoustic waves, such as water-based cooling systems for high-heat-generating processor chips, by tuning the vibration frequency and amplitude, as well as the surface wettability, to obtain the desired performance.

Mitigation of subsurface damage in potassium dihydrogen phosphate (KDP) crystals with a novel abrasive-free jet process

This study presents a novel abrasive-free jet process that can be used to mitigate the lattice misaligned structure induced by mechanical stresses in potassium dihydrogen phosphate (KDP) crystal subsurface. This method makes use of a thermodynamically and kinetically stable ionic liquid microemulsion that contains nanometer range water droplets evenly dispersed in the non-aqueous carrier liquid. The sprayed out nanoscale droplets remove material through microscale dissolution without introducing new residual stress. Grazing incidence X-ray diffraction was used to evaluate the subsurface structure and to validate the mitigating performance. The experimental results show that the novel mitigation method can effectively reduce the thickness of the deformed layer, as well as reduce the surface roughness. This approach ultimately provides a potential path to extend the lifetime of highly valuable and difficult to grow large KDP crystals.

Impact of Encapsulation on in vitro and in vivo Performance of Volatile Nanoscale Phase-Shift Perfluorocarbon Droplets

Phase-shift droplets can be converted by sound from low-echogenicity, liquid-core agents into highly echogenic microbubbles. Many proposed applications in imaging and therapy take advantage of the high spatiotemporal control over this dynamic transition. Although some studies have reported increased circulation time of the droplets compared with microbubbles, few have directly explored the impact of encapsulation on droplet performance. With the goal of developing nanoscale droplets with increased circulatory persistence, we first evaluate the half-life of several candidate phospholipid encapsulations in vitro at clinical frequencies. To evaluate in vivo circulatory persistence, we develop a technique to periodically measure droplet vaporization from high-frequency B-mode scans of a mouse kidney. Results show that longer acyl chain phospholipids can dramatically reduce droplet degradation, increasing median half-life in vitro to 25.6 min—a 50-fold increase over droplets formed from phospholipids commonly used for clinical microbubbles. In vivo, the best-performing droplet formulations showed a median half-life of 18.4 min, more than a 35-fold increase in circulatory half-life compared with microbubbles with the same encapsulation in vivo. These findings also point to possible refinements that may improve nanoscale phase-shift droplet performance beyond those measured here.

Wetting Behaviors of a Nano-Droplet on a Rough Solid Substrate under Perpendicular Electric Field.

Molecular dynamic simulations were adopted to study the wetting properties of nanoscale droplets on rough silicon solid substrate subject to perpendicular electric fields. The effect of roughness factor and electric field strength on the static and dynamic wetting behaviors of a nano-droplet on a solid surface was investigated at the molecular level. Results show that the static contact angle tends to decrease slightly and show small difference with the increase of roughness factor, while it shows an obvious increase for the ramp-shaped surface because the appearing bottom space reduces the wettability of solid surface. Additionally, under the electric field, a nano-droplet was elongated in the field direction and the equilibrium contact angle increases with the increase of electric field strength. The nano-droplet was completely stretched to be column-shaped at a threshold value of the field. Besides, accompanied by the shape variation of water droplets, the molecular dipole orientations of water molecules experience a remarkable change from a random disordered distribution to an ordered profile because of the realignment of water molecules induced by electric fields.