3D Printing of <em>In Vitro</em> Hydrogel Microcarriers by Alternating Viscous-Inertial Force Jetting

Microcarriers are beads with a diameter of 60-250 &#181;m and a large specific surface area, which are commonly used as carriers for large-scale cell ...

Tsinghua University

Biomanufacturing and Rapid Forming Technology Key Laboratory of Beijing

Many self-assembly approaches of colloidal monolayers have flourished but with some shortages, such as complexity, time-consumption, parameter sensitivity, and high-cost. This paper presents a facile, rapid, well-controlled, and low-cost method to prepare monolayers by directly adding silica particle suspensions containing water and ethanol to different liquids. A detailed analysis of the self-assembly process was conducted. The particles dove into water firstly, then moved up under the effect of the buoyancy and the tension gradient. The tension gradient induced the Marangoni convection and the relative motion between the water and the particles. At last, the particles were adsorbed at the air-water interface to minimize the free energy. The quality of the monolayers depended on the addition of sodium dodecyl sulfonate or ethanol in the water subphase. An interfacial polymerization of ethyl 2-cyanoacrylate was used to determine the contact angles of the particles at different subphase surfaces. The value of the detachment energy was positively associated with the contact angle and the surface tension. When the detachment energy decreased to a certain value, some particles detached from the surface, leading to the formation of a quasi-double layer. We also observed that the content of ethanol in suspensions influenced the arrangement of particles.

A Facile Interfacial Self-Assembly of Crystalline Colloidal Monolayers by Tension Gradient.

Oil leakage and the discharge of oil/water mixtures by domestic and industrial consumers have caused not only severe environmental pollution and a threat to all species in the ecosystem but also a huge waste of precious resources. Therefore, the separation of oil/water mixtures, especially stable emulsion, has become an urgent global issue. Recently, materials containing a special wettability feature for oil and water have drawn immense attention because of their potential applications for oil/water separation application. In this paper, we systematically summarize the fundamental theories, separation mechanism, design strategies, and recent developments in materials with special wettability for separating stratified and emulsified oil/water mixtures. The related wetting theories that unveil the physical underlying mechanism of the oil/water separation mechanism are proposed, and the practical design criteria for oil/water separation materials are provided. Guided by the fundamental design criteria, various porous materials with special wettability characteristics, including those which are superhydrophilic/underwater superoleophobic, superhydrophobic/superoleophilic, and superhydrophilic/in-air superoleophobic, are systemically analyzed. These superwetting materials are widely employed to separate oil/water mixtures: from stratified oil/water to emulsified ones. In addition, the materials that implement the demulsification of emulsified oil/water mixtures via the ingenious design of the multiscale surface morphology and construction of special wettability are also discussed. In each section, we introduce the design ideas, base materials, preparation methods, and representative works in detail. Finally, the conclusions and challenges for the oil/water separation research field are discussed in depth.

Separation Mechanism and Construction of Surfaces with Special Wettability for Oil/Water Separation.

Self-assembly of two types of particles into the binary colloidal crystals (BCCs) leads to the peculiar features which the monocomponent colloidal crystals do not possess. However, the self-assembly methods of the BCCs are still limited.

Interfacial tension gradient driven self-assembly of binary colloidal particles for fabrication of superhydrophobic porous films.

The secreted mucilage trails of the diatom Navicula sp. in the process of motility were studied by scanning electron microscopy (SEM), transmission electron microscope (TEM), atomic force microscopy (AFM) and Raman spectra etc. Contrary to previous studies, force measurement was taken directly on the mucilage trails of live cells using the method of in situ force mapping by AFM. The retraction force curve presented an increased tip-substrate peak and a small saw-tooth pattern tip-mucilage peak. Especially, same measurements on various substrates with different surface energy revealed that the mucilage trails actually functioned as a medium increasing the adhesive force between the diatom and substrates, which is crucial to diatom's adhesion and locomotion. In addition, the mechanical properties of mucilage trails were quite different from mucilage strands in the maximum adhesive force and the maximum polymer extension length. Raman spectra indicated the difference in compositions that both of the two kinds of mucilages had proteins and polysaccharide, but the mucilage strands contained some other components with C=O, -CH- and -CH asymmetric and symmetric stretches. This research hammers out more precise information about mucilage trails which would be useful in terms of diatom motility and biofouling prevention.

Contribution of frustules and mucilage trails to the mobility of diatom Navicula sp.

Transportation and position control of objects on the surface of liquids is an important part of automation. To drive an object on the surface of a liquid, many methods have been proposed. However, these methods mainly focus on the driving of the object itself, and it is still difficult to precisely control its position. In our study, we propose a new method that uses vapor released from a suspended drop to achieve precise position control and transport of different types of objects at the air-liquid interface. These objects can be a plastic plate, a liquid marble, or an oil drop. The mechanism for controlling objects is that vapor released from a suspended drop causes a surface tension gradient around the object. When the vapor dissolves on the surface of a liquid, the surface tension of the liquid increases. Due to the surface tension gradient, the object moves from the surrounding area to the area below the suspended drop and follows the motion of the suspended drop with the trajectory of a letter. To show that the position of the objects can be precisely controlled by our method, we control the object on the center of a circle, and the maximum offset distance from the center of the circle is less than 3 mm. In addition, we also use vapor released from a suspended drop to transport an oil drop close to an object. After the drop adhered with the object, the object is driven by the oil drop. Compared with other methods that drive the motion of objects by reducing the surface tension of a liquid, our method is easy and the position of objects can be precisely controlled.

Vapor-Driven Transport of Different Types of Objects at the Air-Liquid Interface.

Although artificial superhydrophobic materials have extensive and significant applications in antifouling, self-cleaning, anti-icing, fluid transport, oil/water separation, and so forth, the poor robustness of these surfaces has always been a bottleneck for their development in practical industrial applications. Here, we report a facile, economical, efficient, and versatile strategy to prepare environmentally friendly, mechanically robust, and transparent superhydrophobic surfaces by combining adhesive and hydrophobic paint, which is applicable for both hard and soft substrates. The coated substrates exhibit excellent superhydrophobic property and ultralow adhesion with water (contact angle ≈ 160° and sliding angle <2°). Additionally, the coated surface maintained its superhydrophobicity even after 325 sandpaper abrasion cycles, showing remarkable mechanical robustness. Furthermore, the coated surfaces were applied to separate oil/water mixtures because of their unique characteristics of being simultaneously superhydrophobic and superoleophilic. In addition, it is believed that this fabrication method is significant, promising, and feasible for mass production of superhydrophobic surfaces for industrial applications.

Development of Durable, Fluorine-free, and Transparent Superhydrophobic Surfaces for Oil/Water Separation.

Generally, interactions of oil drops at the air-liquid interface mainly have two features, namely, attraction and repulsion. However, in our study, we find that the oil drops at the air-liquid interface have other interacting features, that is, the atomic-like motion and the "capture" motion. For the atomic-like motion, oil drops attract each other at a long distance, but repel when they are about to come into contact with each other. For the "capture" motion, a big oil drop can actively "capture" oil droplets like a zooplankton. In our research, we analyze interfacial forces among the oil drops. Based on the experiments and analyses, we demonstrate that the atomic-like motion of oil drops is mainly due to the lateral capillary force and the surface tension force, and the "capture" motion is mainly due to the unbalanced impact force of flow fluid around the drops. In addition, based on our results, we use the oil drops to perform many functions at the air-liquid interface. For example, the oil drops can drive an object with linear and rotational motion. When a carbon tetrachloride drop is suspended above the air-liquid interface, it can be used to control an oil droplet to pass through serpentine grooves and obstacles. In addition, the suspended carbon tetrachloride drops also can be used to rank multiple droplets with a special shape. Based on the results, our study makes it possible to use oil drops to transport materials, drive objects, and even collect droplets at the air-liquid interface.

Life-Like Motion of Oil Drops at the Air-Liquid Interface.

The directional propulsion of liquid droplets at the nanoscale is quite an interesting topic of research in the fields of micro/nano-fluidics, water filtration, precision medicine, and cooling of electronics. In this study, the unidirectional spontaneous transport of a water nanodroplet on a solid surface with a multi-gradient surface (MGS) inspired by natural species is modeled and analyzed using molecular dynamics (MD) simulations. There are three different MGSs considered in this study containing different wedge angles of the hydrophilic region of the solid surface. The MGSs contain two regions: a hydrophilic wedge-shaped region with a constant surface energy parameter equal to 50 meV and a hydrophobic region with a tuned surface energy parameter. The energy parameter of the hydrophobic region is set equal to 1, 5, 10, 20, 30, and 40 meV in order to alter the intensity of the wettability gradient of the two surfaces and its effect on the propulsion of the water nanodroplet is analyzed. Furthermore, three different sizes of water droplets containing 6000, 8000, and 10 000 water molecules are also used in this study and their effect on the transport behavior of the water nanodroplet is also measured. Moreover, two different designs on a solid surface with a continuous wettability gradient are modelled and the impact of solid surface geometry on the transport of the water droplet is calculated by means of mean square displacement (MSD) and average velocity data. In addition, the wedge-shaped surface is found to be more superior to the parallel-shaped surface for the spontaneous propulsion of the water droplet.

Spontaneous propulsion of a water nanodroplet induced by a wettability gradient: a molecular dynamics simulation study.

Cervical cancer induced by human papillomavirus (HPV) causes severe morbidity worldwide. Although cervical conization has been widely accepted as the most conventional surgery against cervical cancer, tissue defects and high recurrence rates have a significant negative impact on women's mental and physical health. Herein we developed an implantable, personalized cervical implant with drug release function using 3D printing technology. The cervical implant was designed in cone-shape with hieratical porous structures according to the clinical data, 3D-printed using polyurethane by low-temperature deposition manufacturing (LDM), and finished by lyophilization. Anti-HPV protein was loaded into the porous structure under negative pressure afterwards. Elastic biomedical polyurethane and the porous structure ensured that these cervical implants were equipped with tailored mechanical properties comparable to physiological cervix tissue. Cytotoxicity and cytocompatibility tests indicated that these 3D-printed cervical implants supported cell adhesion and growth. More importantly, the cervical implants with regulated pores could help to quantitatively control the loading and release of anti-HPV protein to inhibit dissociative viruses near the cervix validly. As a result, the 3D-printed cervical implants in the present study showed considerable potential for use as functional tissue implants against HPV infection after cervical conization.

Design, modeling and 3D printing of a personalized cervix tissue implant with protein release function.

Although various superhydrophobic/superoleophilic porous materials have been developed and successfully applied to separate water-in-oil emulsions through the size-sieving mechanism, the separation performance is restricted by their nanoscale pore size severely. In this study, the wettability of underoil water on fumed silica was experimentally observed, and the underlying mechanism was investigated by carrying out theoretical analysis and molecular dynamic (MD) simulations. Further, we present a novel, facile, and an inexpensive technique to fabricate an underoil superhydrophilic metal felt with microscale pores for the separation of water-in-oil emulsions using SiO nanoparticles (NPs) as building blocks. The as-prepared underoil superhydrophilic coating is closed-packed and ultrathin (the thickness is approximately hundreds of nanometers), as well as capable of being coated on a metal felt with complex structures without blocking its pores. The as-prepared metal felt could adsorb water droplets directly from oil, which endowed it with the ability to separate both surfactant-free and surfactant-stabilized water-in-oil emulsions with high separation efficiency up to 99.7% even though its pore size is larger than that of the emulsified droplet. The filtration flux for the separation of span 80-stabilized emulsion is up to ∼4000 L·m·h. Its separation performance is better than most of the other traditional membranes and superwettable materials used for the separation of water-in-oil emulsions. Moreover, the as-prepared metal felt retained outstanding separation performance even after 30 cycles of use, which demonstrated its excellent reusability and durability. Additionally, the distinctive wettability of underoil superhydrophilicity endued coated metal felt with superior antifouling properties toward crude oil. Overall, this study not only provides a new perspective on separating water-in-oil emulsions but also gives a universal approach to develop unique wettability surfaces.

Underoil Superhydrophilic Metal Felt Fabricated by Modifying Ultrathin Fumed Silica Coatings for the Separation of Water-in-Oil Emulsions.

Although increasing superwetting membranes have been developed for separating oil-water emulsions based on the "size-sieving" mechanism, their pores are easily blocked and fouled by the intercepted emulsified droplets, which would result in a severe membrane fouling issue and a sharp decline in flux. Instead of droplet interception, a fiber-based coalescer separates oil/water emulsions by inducing the emulsified droplets to coalesce and transform into layered oil/water mixtures, exhibiting an ability to work continuously for a long time with high throughput, which makes it a promising technology for emulsion treatment. However, the underlying mechanism of the separation process is not well understood, which makes it difficult to further improve the separation performance. Hence, in this work, the dynamic behaviors of water-in-oil emulsified droplets on the surface of the coalescing fiber were numerically investigated based on the phase-field model. The attachment, transport, and detachment behaviors of droplets on fibers were directly observed, and the effects of fiber wettability, orientation, arrangement, and fluid speed were studied in detail. First, it was observed that the droplets will move downstream along the fiber surface under the effect of fluid shear, and the large droplets tend to coalesce with their downstream small droplets on the same fiber surface because they move faster compared to the small droplets. Second, it was found that the emulsified droplet will spontaneously transport to the intersection of two angled fibers under the drive of asymmetric Laplace pressure, which demonstrated that the emulsified droplets tend to gather at the intersection of fibers when permeating through a coalescing medium. Third, it was found that the detachment behaviors of droplets from the fiber surface are strongly affected by their size, fiber wettability, and fluid velocity. In addition, the results of our simulation show that the backside of two closely attached fibers can further inhibit the detachment of droplets. We truly believe that our research results are of significance to optimize the parameters of a fiber-based coalescer for separating oil-water emulsions and to develop novel oil/water separators.

Simulation Study on the Dynamic Behaviors of Water-in-Oil Emulsified Droplets on Coalescing Fibers.

A binary mixture was used during injection with one water-miscible component and the other water-immiscible, which can help particles to migrate toward and then self-assemble at the interface.

Tension gradient-driven oil/water interface rapid particle self-assembly and its application in microdroplet motion control.

Infectious disease outbreaks such as the COVID-19 (coronavirus disease 2019) pandemic call for rapid response and complete screening of the suspected community population to identify potential carriers of pathogens. Central laboratories rely on time-consuming sample collection methods that are rarely available in resource-limited settings.

Ding Weng

Biomanufacturing Center,
Dept. of Mechanical Engineering,
Biomanufacturing Center, Dept. of Mechanical Engineering

Tsinghua University

3D Printing of In Vitro Hydrogel Microcarriers by Alternating Viscous-Inertial Force Jetting

Ding Weng

.css-o250i3{font-size:18px;font-family:Open Sans,sans-serif;line-height:21.6px;}Biomanufacturing Center,Dept. of Mechanical Engineering,Biomanufacturing Center, Dept. of Mechanical Engineering

Tsinghua University

3D Printing of In Vitro Hydrogel Microcarriers by Alternating Viscous-Inertial Force Jetting

Biomanufacturing Center,
Dept. of Mechanical Engineering,
Biomanufacturing Center, Dept. of Mechanical Engineering