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Dr. Wei Wu has received awards from many national societies for the originality and quality of his projects. He has authored 70 peer-reviewed papers in international journals.",coeditorOneBiosketch:"A pioneering researcher in obstetrics and holder of three registered patents. Dr. Qiuqin Tang's research interests include genetic and epigenetic risk factors of reproductive and developmental health. She has authored over 20 papers in international journals.",coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"178661",title:"Dr.",name:"Wei",middleName:null,surname:"Wu",slug:"wei-wu",fullName:"Wei Wu",profilePictureURL:"https://mts.intechopen.com/storage/users/178661/images/system/178661.jpeg",biography:"Dr. Wei Wu is an associate professor and associate department\nchair in the Department of Toxicology, Nanjing Medical University, China, where he received his Ph.D. in Toxicology in 2012.\nHe was a guest researcher at the National Institute of Environmental Health Sciences (NIEHS) between 2017 and 2018. Dr.\nWu is a member of different national and international societies\nin the fields of human reproduction and toxicology and has\nreceived awards from many national societies for the originality and quality of his\nprojects. Dr. Wu has authored seventy-three peer-reviewed papers in international\njournals. He has edited four books and collaborated on ten others as well as seventeen patents and in the organization of three international conferences. He is a\nreviewer for ninety-eight journals.",institutionString:"Nanjing Medical University",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"4",totalChapterViews:"0",totalEditedBooks:"4",institution:{name:"Nanjing Medical University",institutionURL:null,country:{name:"China"}}}],coeditorOne:{id:"184798",title:"Ms.",name:"Qiuqin",middleName:null,surname:"Tang",slug:"qiuqin-tang",fullName:"Qiuqin Tang",profilePictureURL:"https://mts.intechopen.com/storage/users/184798/images/13334_n.jpg",biography:"Qiuqin Tang is an attending doctor of The Women’s Hospital of Nanjing Medical University (Nanjing Maternity and Child Health Care Hospital). Her research interests include genetic and epigenetic risk factors of reproductive and developmental health. She has authored over 20 papers in international journals such as EBioMedicine, Clinical Epigenetics, Molecular Human Reproduction, Scientific Reports, and European Journal of Endocrinology. She has collaborated in four books and three patents. She is the Editor-in-Chief of Journal of Woman\\'s Reproductive Health, and editor of many other journals including Journal of Gynecology and Obstetrics, and Journal of Gynecology and Obstetrics Forecast.",institutionString:"Nanjing Medical University",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"4",totalChapterViews:"0",totalEditedBooks:"0",institution:{name:"Nanjing Medical University",institutionURL:null,country:{name:"China"}}},coeditorTwo:{id:"48837",title:"Prof.",name:"Panagiotis",middleName:null,surname:"Tsikouras",slug:"panagiotis-tsikouras",fullName:"Panagiotis Tsikouras",profilePictureURL:"https://mts.intechopen.com/storage/users/48837/images/system/48837.jpg",biography:"Dr. Panagiotis Tsikouras is a specialist in obstetrics-gynecology,\nperinatal medicine, and contraception at the School of Medicine,\nDemocritus University of Thrace, Greece. He is also the headmaster of the Family Planning Centre and Gynecological Cytology\nLaboratory at the same university. Dr. Tsikouras is a fellow of the\nInternational Academy of Clinical and Applied Thrombosis/Hemostasis. His scientific activities focus on paediatric and adolescence medicine, gynecological oncology, high-risk pregnancies. He is a reviewer for several international journals and has numerous scientific publications to his credit, including papers and book chapters. He has also contributed to international and national guidelines on coagulation and thrombosis in obstetrics-gynecology.",institutionString:"Democritus University of Thrace, Komotini",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"11",totalChapterViews:"0",totalEditedBooks:"1",institution:{name:"Democritus University of Thrace",institutionURL:null,country:{name:"Greece"}}},coeditorThree:{id:"290374",title:"Prof.",name:"Werner",middleName:null,surname:"Rath",slug:"werner-rath",fullName:"Werner Rath",profilePictureURL:"https://mts.intechopen.com/storage/users/290374/images/system/290374.jpg",biography:"Dr. Werner Rath is a specialist in obstetrics and gynecology, gynecologic oncology, perinatal medicine, and hemostaseology. He\nis currently a professor in the Gynecology and Obstetrics Faculty\nof Medicine, University of Kiel, Germany, and honorary doctor\nat the Democritus University of Thrace, Alexandroupoli University Hospital He previously served as chief of the Department\nof Gynecology and Obstetrics at University Hospital RWTH Aachen,\nGermany. Dr. Rath is a reviewer for numerous journals and chief editor of Geburtshilfe und Frauenheilkunde (GebFra). He has several publications, including thirteen\nbook chapters, to his credit.",institutionString:"Kiel University",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"4",totalChapterViews:"0",totalEditedBooks:"0",institution:{name:"Kiel University",institutionURL:null,country:{name:"Germany"}}},coeditorFour:{id:"299669",title:"Prof.",name:"Georg-Friedrich",middleName:null,surname:"Von Tempelhoff",slug:"georg-friedrich-von-tempelhoff",fullName:"Georg-Friedrich Von Tempelhoff",profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:"St. Vinzenz Krankenhaus",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"1",totalChapterViews:"0",totalEditedBooks:"0",institution:null},coeditorFive:null,topics:[{id:"16",title:"Medicine",slug:"medicine"}],chapters:[{id:"79159",title:"Open Fetal Surgery and Fetoscopic Repair in Spina Bifida and Myelomeningocele in Romania",slug:"open-fetal-surgery-and-fetoscopic-repair-in-spina-bifida-and-myelomeningocele-in-romania",totalDownloads:61,totalCrossrefCites:0,authors:[null]},{id:"79947",title:"Endoscopic Approach to Ectopic Pregnancy",slug:"endoscopic-approach-to-ectopic-pregnancy",totalDownloads:59,totalCrossrefCites:0,authors:[null]},{id:"80212",title:"Diagnosis of Ectopic Pregnancy",slug:"diagnosis-of-ectopic-pregnancy",totalDownloads:74,totalCrossrefCites:0,authors:[null]},{id:"80756",title:"Medical Management of Ectopic Pregnancy",slug:"medical-management-of-ectopic-pregnancy",totalDownloads:32,totalCrossrefCites:0,authors:[null]},{id:"81269",title:"Fetal Craniospinal Malformations: Aetiology and Diagnosis",slug:"fetal-craniospinal-malformations-aetiology-and-diagnosis",totalDownloads:13,totalCrossrefCites:0,authors:[null]},{id:"81570",title:"Prenatal Diagnosis of Diaphragmatic Hernia",slug:"prenatal-diagnosis-of-diaphragmatic-hernia",totalDownloads:15,totalCrossrefCites:0,authors:[null]},{id:"81868",title:"Prenatal Diagnosis: The Main Advances in the Application of Identification of Biomarkers Based on Multi-Omics",slug:"prenatal-diagnosis-the-main-advances-in-the-application-of-identification-of-biomarkers-based-on-mul",totalDownloads:0,totalCrossrefCites:0,authors:[null]},{id:"81273",title:"Ectopic Pregnancy after Ipsilateral Salpingectomy",slug:"ectopic-pregnancy-after-ipsilateral-salpingectomy",totalDownloads:13,totalCrossrefCites:0,authors:[null]}],productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"},personalPublishingAssistant:{id:"278926",firstName:"Ivana",lastName:"Barac",middleName:null,title:"Ms.",imageUrl:"https://mts.intechopen.com/storage/users/278926/images/8058_n.jpg",email:"ivana.b@intechopen.com",biography:"As an Author Service Manager my responsibilities include monitoring and facilitating all publishing activities for authors and editors. 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Venkateswarlu",coverURL:"https://cdn.intechopen.com/books/images_new/371.jpg",editedByType:"Edited by",editors:[{id:"58592",title:"Dr.",name:"Arun",surname:"Shanker",slug:"arun-shanker",fullName:"Arun Shanker"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},chapter:{item:{type:"chapter",id:"70457",title:"Catalytic Micro/Nanomotors: Propulsion Mechanisms, Fabrication, Control, and Applications",doi:"10.5772/intechopen.90456",slug:"catalytic-micro-nanomotors-propulsion-mechanisms-fabrication-control-and-applications",body:'Movement is crucial for all different types of lives existing in both macroscopic and micro-/nanoscopic environments. Nature has developed smart and high-efficiency biomolecular motor proteins through such many years of biological evolution and has employed them in numerous biological processes and cellular activities [1, 2, 3]. For instance, bacteria are able to propel themselves forward with the aid of rotary flagellar nanomotors, as shown in Figure 1A [1]. Moreover, linear biomolecular motor proteins, such as kinesin, myosin, and dynein, are capable of harvesting energy from hydrolyzing adenosine triphosphate (ATP) into adenosine diphosphate (ADP) and phosphate (Pi) molecule for lateral motion along corresponding tracts, as shown in Figure 1B [2]. In addition, biological cells are equipped with intelligent biomolecular engines (ATPase), which are demanded to generate biological fuel ATP, as shown in Figure 1C [3].
(A) Schematic diagram of the architecture of the bacterial flagellar motor. (B) The twin heads of kinesin motor protein alternately bind to the microtubules so that the protein motor moves forward. (C) Schematic diagram of ATPase. Copyright 2012, Elsevier. Copyright 2004, IEEE Xplore Digital Library. Copyright 2000, The Royal society Publishing.
Micro-/nanomotors are micro-/nanoscale devices, which possess the ability to convert chemical energy into mechanical force or movement [4]. Evolution bestows biomolecular protein motors with fascinating abilities to harness energy from living environments for autonomous motion
The research of synthetic self-propelled micro-/nanomotors has rapidly developed in last few decades [4, 5, 6, 7, 8, 9]. Several advanced developments and excellent contributions had been made in this field. Although the bright future of this research area can be expected, some major existing challenges are still remained to be solved. The design, fabrication, and characterization of functional micro-/nanomotors require some innovative approaches and ideas to realize. Fabricating micro-/nanomotors with individual functional parts, smartly and precisely controlling motors are still extremely challenging. Hereby, a complete understanding of the physiochemical mechanism is necessary. To realize better control of micro-/nanomotors in the future, an industrial level of functional micro-/nanomachinery could be achieved. Despite of the significant development and advances in micro-/nanomotors, challenges are still remained to find specific relevant applications, such as biologically compatible fuels, etc.
Meanwhile, micro-/nanomotors have a wide variety of applications, including cargo towing, water cleaning, chemical sensors, biomedical applications, etc. [5, 7, 8, 9]. Advanced forms of micro-/nanomotors may stimulate and benefit other research. However, designing and powering micro-/nanomotors can be considered as a significant challenge in today’s nanotechnology research. Hence, it is much beneficial for us to learn the state of the art of synthetic micro-/nanomotors and improve them in this research field. In this chapter, the reported work on the propulsion mechanisms, fabrication methods, propulsion controlling, and applications of synthetic self-propelled platinum-based micro-/nanomotors will be presented and discussed.
Whitesides and his colleagues firstly reported the motion of a millimeter-scale object, which was composed of a piece of platinum (Pt)-coated porous glass filter mounted on a thin polydimethylsiloxane (PDMS) plate using a stainless steel pin, as shown in Figure 2 [10]. The assembled object was immersed into hydrogen peroxide (H2O2) solution. Pt catalyzes H2O2 decomposition to generate oxygen (O2) bubbles releasing from its surface, which reversely induced a recoil force to propel the object moving forward. This is the foundation in this research field. In micro-/nanoscale regime, only asymmetric particles can realize autonomous propulsion. Based on this, researchers focused on two aspects: shape and material compositions of micro-/nanomotors for breaking the symmetry, and various types of micro-/nanomotors were invented. Meanwhile, there were different mechanisms proposed to explain the propulsion phenomena, depending on the shapes (e.g., wires, rods, Janus spheres, and tubular jets) and material compositions of micro-/nanomotors [4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17].
(A) Schematic diagram of the propulsion of a millimeter-scale object. A thin plate (1–2 mm in thickness and 9 mm in diameter) was assembled from PDMS in a desired shape, and specified faces were rendered as hydrophilic by plasma oxidation. A 2 × 2 mm2 piece of porous glass filter (one side covered with Pt) was mounted on the PDMS plate by using a stainless steel pin. (B) A diagram illustrating self-assembly by capillary interactions. Copyright 2002, Wiley Online Library.
In the past decades, a variety of micro-/nanomotors have been envisioned to explore the concept of self-electrophoresis propulsion, especially micro-/nanowires, rods, and Janus spheres. In self-electrophoresis, micro-/nanomotors produce a locally distributed electric field through chemical gradients and propel forward in respond to this self-produced electric field, and they do not respond to an external electric field.
Electrophoresis describes the movement of micro-/nanoscale particles in a fluid. In dielectrophoresis, if a micro-/nanoparticle would realize autonomous self-propulsion, the micro-/nanoparticle must contain at least two different metals and acts as a self-contained electro-chemical cell. For instance, a micro-/nanorod is composed of Pt and gold (Au), Au serves as the cathode and Pt is the anode, as shown in Figure 3 [6].
Schematic representation of dielectrophoresis (bipolar electrochemical) mechanism for the propulsion of an Au-Pt micro-/nanomotor in the presence of H2O2. The mechanism involves an internal electron flow from one end to the other end of the motor, along with the migration of protons in the double layer surrounding the motor. Copyright 2006, ACS Publications.
The oxidation of H2O2 at the Pt side (anode) of the rod generates negatively charged electrons (
In self-electrophoresis, the charged micro-/nanoparticles propel forward in a self-generated electric field resulting from an uneven distribution of ions. The velocity
Self-diffusiophoresis is a propulsion phenomenon in which the movement of particles is induced by a concentration gradient of the reaction products. This propulsion mechanism is more commonly employed in spherical Janus micro-/nanomotors, as shown in Figure 4 [11, 12]. In this system, the catalyst (Pt) is located at one side of the micro-/nanomotor; the reaction products (H2O and O2) preferentially accumulate at the site of the catalyst. Hence, a concentration gradient is produced along the surface of the micro-/nanomotor. As the reaction products reach a certain point, the local concentration is higher and the products start to diffuse away from the catalyst, which in turn produces a force leading to the movement of the micro-/nanomotor.
Schematic diagram of a micro/nanomotor propelling under the diffusiophoresis propulsion mechanism. Copyright 2009, Wiley Online Library. Copyright 2011, Frontiers Journals of Higher Education Press.
Surface tension gradient along an interface can result in an imbalanced force and further produce flow, which is well known as the “Marangoni effect.” This motion mechanism has been employed to explain the propulsion of the micro-/nanomotors, and the model was firstly reported by Crespi, Mallouk, and Sen, as shown in Figure 5 [13]. As H2O2 is decomposed at the Pt side of Au-Pt nanorods to produce H2O and O2, leading to an interfacial tension created near the surface of Pt is lower due to a larger quantity of O2 generated. The surface tension difference between the Pt side and the Au side produces a force to thrust the micro-/nanomotor propelling forward.
Schematic illustration of a Pt-Au nanorod representing the dimensions used in the calculation of interfacial force. The parameter f is the length ratio of Pt. Copyright 2004, ACS Publications.
In this model, it is proposed that the velocity
where S, R,
One of the potential applications of micro-/nanomotors is to be used in diagnostics and biomedicine; there is a demand to develop propulsion mechanisms which can be biocompatible. Ultrasound operates in a range of frequency above 20 kHz, which is biocompatible [5]. Hence, ultrasound is a promising technique for propelling micro-/nanomotors (wires/rods and tubular jets) in biomedical applications. The micro-/nanomotor propelled by ultrasound was firstly reported by Sen’s group in 2012, as shown in Figure 6 [5]. In this system, metallic microrods are suspended in water surrounded by an acoustic chamber. A vertical standing wave levitates the microrods to a plane at the midpoint of the cell resulting from the lowest pressure. In that plane, the metallic microrods behave axial propulsion at speeds up to 200 μm/s in water. The microrods also assemble into patterns in the nodal plane resulting from nodes and antinodes among the plane. The composition of the microrods was observed to effectively affect their propulsion, with only metallic microparticles demonstrating fast axial motion.
Self-acoustophoresis mechanism: asymmetrically shaped metallic microrods are triggered by an ultrasonic standing wave at MHz frequency. Copyright 2012, ACS Publcations.
Temperature gradient could introduce the motion of micro-/nanoparticles (micro-/nanowires, rods, and Janus spheres). This phenomenon is called thermophoresis or the “Soret effect.” Recently, the propulsion of micro-/nanomotors induced by self-generated temperature gradient has been investigated, as shown in Figure 7.
Self-thermophoretic microparticles. (A) Au-capped SiO2 microspheres undergoing autonomous propulsion resulting from the “Soret effect” in a defocused laser beam. (B) Permalloy-capped SiO2 particles moving by self-thermophoresis in an AC magnetic field. Copyright 2010, APS Publications. Copyright 2012, ACS Publications.
Jiang et al. studied self-thermophoresis at the single particle level (Figure 7A) in 2010 [14]. Janus silica (SiO2) microspheres half-coated with Au were irradiated in water by using a defocused laser beam at 1064 nm. Absorption of laser by the thin Au layer generated heat, resulting in a local temperature gradient (∼2 K across particles) which produced thermophoresis. After that, Baraban et al. applied an alternating current (AC) magnetic field to heat up and down permalloy-capped SiO2 particles in solution and viewed autonomous movement, as shown in Figure 7B [15].
Short heat pulses have also been applied to modulate the speed of micro-/nanomotors. Au-Pt nanowires subjected to elevated temperatures were observed to propel forward extremely faster than those at room temperature. For instance, an average speed of 45 μm/s was obtained for nanowires at 65°C compared with 14 μm/s at 25°C. The speed increasing could be resulted from the reduction of the solution’s viscosity and the temperature dependency of the electrochemical process. The utilization of heat pulses is an extremely reversible process, after incorporated with magnetic steering, which will enable a more advanced spatial and temporal control, with the capability to modulate both the direction and the speed.
Bubble propulsion is possibly the most commonly studied mechanism in the field of micro-/nanomotors, which can be suitable for motors with any shapes as long as the motors are decorated with catalysts. The motion of the motors is produced by the releasing of micro-sized bubbles from the decomposition of fuel catalyzed by the catalyst. The most extensively studied instances of bubble-propelled micro-/nanomotors are those decorated with Pt as a catalyst to decompose H2O2 into H2O and O2 bubbles, as shown in Figure 8 [16, 17].
Examples of bubble propelled micromotors. (A) Schematic illustration of a tubular micro-/nanomotor’s movement by the bubble propulsion mechanism. (B) Janus Pt-SiO2 spheres moving in H2O2. Copyright 2014, RSC Publications. Copyright 2009, AIP Publications.
Bubble propulsion originates from the spontaneous decomposition of a fuel stimulated by a catalyst into micron-sized gas bubbles, whose detachments from the micro-/nanomotor’s surface produce a recoil force to thrust the movement of the motors in the direction away from the catalyst. These motors, whose size ranging from a few micrometers to hundreds of micrometers, can realize powerful movement with considerable speed. In bubble-propelled micro-/nanojets, Solovev and his colleagues reported that the speed of the micro-/nanojets was related to the bubble’s detachment frequency and radius, with the deviations at large values resulted from the potential collisions between bubbles, which diminished the distance traveled by the bubbles within the tube and limits the detaching stage. They concluded that the dynamics of micro-/nanojets is influenced by their shapes, the fuel composition, and the viscosity of the medium.
Artificial micro-/nanomotors could offer a significant advance in the field of miniaturized devices. However, a major challenge in artificial micro-/nanomotor field is the synthesis of such tiny devices with high quality and reliability. Relying on the intended applications, different synthesis techniques must be taken into account, since each specifically shaped micro-/nanomotor demands a specialized synthesis technique as well as defines the desired propulsion mechanism. The rapid developing of nanotechnology has resulted in various techniques and strategies for the synthesis of micro- and nanoscale motors. The purpose of this section is to present versatile schemes to the synthesis of micro-/nanomotors. The synthesis strategies and the factors that ought to be considered in the design of micro-/nanomotors are including the shapes, compositions, and distributions of materials, and functionalization. By highlighting the progresses that have been achieved in the synthesis of artificial micro-/nanomotors over the last decades, we intend to present the challenges and opportunities facing synthesis and put forward perspectives for the upgrowth of new methods.
Electrochemical deposition is a process that applies external electric current to grow materials and enables the growth of arbitrary three-dimensional (3D) shapes with distinct materials varying from metals to polymers, resulting in the widespread applications of this growth strategy in nanotechnology. The process can be conducted without the requirements of expensive instruments and harsh working environments. Therefore, micro-/nanostructures with diverse dimensions can be grown using this method, especially the micro-/nanowire, micro-/nanorod, and tubular micro-/nanoengines.
Template-assisted electrochemical deposition, as shown in Figure 9, utilizes the pores of a membrane template to grow the required wires and tubes comprising of different materials [18]. Each pore of the template functions as a reactor in which the desired structure is synthesized. Membrane templates commonly used for the synthesis of micro-/nanomotors are track-etched polycarbonate (PC) membranes and porous alumina (AAO) membranes. Relying on the properties of the material and the chemistry of the pore wall, the micro-/nanomotors can be either hollow or solid. Membrane template-assisted electrodeposition provides a relatively low-cost and powerful approach for synthesizing micro-/nanowires, micro-/nanorods, and tubular micro-/nanoengines.
Membrane template-assisted electrochemical deposition of micro-/nanomotors: (a) coating of Au or Ag backing on the membrane template, (b) electrochemical deposition of the sacrificial layer, (c) sequential electrochemical deposition of desired elements, and (d) removal of the backing and sacrificial layer and dissolution of the membrane. Copyright 2015, ACS Publications.
For membrane template-assisted electrodeposition, a layer of Au or silver (Ag) is firstly coated on one side of the membrane by physical vapor deposition (PVD) to play a role of the working electrode. Afterwards, the membrane is assembled in a Teflon plating cell with flat aluminum (Al) foil located against the metal layer to work as a conductive contact for subsequent electrodeposition. Commonly, a sacrificial layer of Ag or copper (Cu) is firstly grown, followed by sequential growth of different required metals. The Ag or Au backing and the sacrificial layer are etched away by chemical etchant or are removed by mechanical polishing. By removing the alumina (Al2O3) membrane in sodium hydroxide (NaOH) solution, the nanowires or nanotubes can be released and obtained after successive rinsing and centrifugation.
The Wang’s and Pumera’s research groups combined electrodeposition widely applied in the growth of nanowire-based micro-/nanomotors with the bubble-propelled tubular micro-/nanojets, as shown in Figure 10 [19, 20, 21, 22, 23, 24]. Two geometries (either cylindrical or conical) can be obtained, entirely relying on the type and geometry of porous template (either PC or AAO). In addition to such metals, the incorporation of polyethylenedioxythiophene (PEDOT), polyaniline (PANI), and polypyrrole (PPy) polymers with Pt generates catalytic microjets. On the other hand, the wall can be incorporated with molecularly imprinted polymers (MIPs) so that alternative recognition cavities can be implemented for the selective separation of biomolecules.
Examples of micro-/nanomotors grown by template-assisted electrochemical deposition. (A) Electrodeposited Ag-Au/Pt and (B) Au/Pt-CNT nanomotors in H2O2. (C, D) Polycarbonate membrane-assisted growth and SEM images of conical PANI/Pt microtubes, respectively. (E) Growth procedures of flexible metallic nanowires with polyelectrolyte hinges after membrane template electrodeposition. (F, G) Anodized AAO membrane-assisted growth and SEM (scanning electron microscopy) images of segmented microtubes, respectively. (H) SEM image of a hinged nanowire. (I) SEM image of a Au/Agflex/Ni nanomotor with flexible central Ag segment. Copyright 2008, Wiley Online Library. Copyright 2008, ACS Publications. Copyright 2011, ACS Publications. Copyright 2007, Nature Publishing Group. Copyright 2013, RSC Publications. Copyright 2010, ACS Publications.
PVD is a vaporization deposition process for coating thin layers of materials. The material from a solid target is firstly vapored by a gaseous plasma or a high-temperature vacuum. Afterwards, the vapor is transferred to the surface of the substrate in vacuum or partial vacuum. Finally, it is condensed to produce thin films. The two most common kinds of PVD procedures are electron beam evaporation and sputtering. Electron beam evaporation is a process that generates an electron beam to evaporate atoms from the target into the gaseous phase, whereas sputtering creates vapor through bombardment of the target by ionized gas, typically argon (Ar). In both strategies, the produced vapor phase is subsequently condensed onto the surface of the substrate.
PVD has been shown to be an effective fabrication method in micro-/nanomotors. Compared with template-assisted electrochemical deposition, PVD has some advantages, such as the ability to coat a wide range of materials, less fabrication processes, easier to operate, and more complicated geometries of micro-/nanomotors can be fabricated. According to the deposition angles, there are two categories of PVD: conventional PVD and dynamical shadowing growth (DAG). In conventional PVD, the substrate is placed parallel to the target and the vapored metal flux is condensed almost vertically onto the substrate. DAG or glancing angle deposition (GLAD) is a PVD strategy in which the vapor is deposited onto a substrate at an oblique angle.
Posner and co-workers reported the fabrication of a bimetallic spherical motor depending on the electrophoretic mechanism for motion, as shown in Figure 11A [25]. Firstly, the microspheres were half-deposited with Au by sputter machine. Afterwards, they were resuspended in water and coated again with Au in random orientation, which was repeated seven or eight times until the whole surface was fully deposited with Au. Finally, the Au-deposited spheres were half-deposited with Pt, which produced bimetallic spherical Janus micromotors that are able to propel forward at velocities comparable to their nanowire counterparts. On the basis of sphere templates, PVD can be employed to synthesize not only spherical Janus motors but also versatile motors with various geometries. Valadares and co-workers studied a catalytic dimer comprising of a Pt half-sphere and a SiO2 sphere. The spheres were firstly deposited with a bilayer of Cr/Pt by using sputter machine, followed by an annealing process, during which the metallic half-shell formed a Pt particle combined with the SiO2 sphere, as shown in Figure 11B [26].
(A) Schematic representation of the synthesis of bimetallic Janus micromotors by conventional PVD. (B) Synthesis of sphere dimers via thermal annealing. (C) Fabrication of asymmetric Pt/Au-coated catalytic micromotors by GLAD. (D) Fabrication of electrophoretic Pt-Au Janus nanoparticles by GLAD. (E) Synthesis procedures of L-shaped Si/Pt nanorod motors by GLAD. (F) Fabrication of catalytic micromotor comprising of a spherical SiO2 colloid with a TiO2 arm deposited asymmetrically with Pt. (G) SEM image of a Pt-Ag-Au shell micromotor synthesized by GLAD. Copyright 2010, ACS Publications. Copyright 2010, Wiley Online Library. Copyright 2010, AIP Publications. Copyright 2014, ACS Publications. Copyright 2007, ACS Publications. Copyright 2004, ACS Publications. Copyright 2013, RSC Publications.
Relying on the substrate rotation during the deposition of an incident vapor and the self-shadowing effect, GLAD offers an easier way to synthesize Janus micro-/nanomotors with complicated geometries. Zhao and his colleagues studied the asymmetric Pt/Au-deposited catalytic micromotors synthesized by GLAD. To get an asymmetric bimetallic deposition, a SiO2 microbeads-coated substrate was rotated to a polar angle after coating of an adhesive titanium (Ti) layer and an Au layer, the subsequent Pt coating left some of the Au layer exposed, as shown in Figure 11C [27]. The propulsion behavior could be regulated by changing the exposed area of the Au layer. Lee and co-workers synthesized a 30 nm Pt/Au Janus nanomotors by GLAD in which Au under fast substrate rotation was deposited onto an array of Pt nanoparticles generated by block copolymer micelle lithography, as shown in Figure 11D [28]. Both of the bimetallic Janus motors depend on the self-electrophoresis mechanism for propulsion.
He and his colleagues demonstrated the synthesis of rotary silicon/Pt (Si/Pt) nanorods, Si/Ag nanorods, and L-shaped Si/Pt where they firstly applied GLAD to synthesize the Si nanorod backbone and then asymmetrically deposited a Pt or Ag layer on one side of the nanorod backbone with a geometric shadowing effect. The L-shaped backbone was fabricated by a high speed of azimuthal rotation of the substrate in the middle of oblique angle deposition, as shown in Figure 11E [29]. By monitoring the substrate rotation and the deposition angle, complex rolling Si/Ag springs can be synthesized. Gibbs and Zhao reported the rotary propulsion of a micromotor comprising of a SiO2 microbead and a titanium dioxide (TiO2) arm with asymmetric Pt deposition. The arms of the micromotors were synthesized on the closely packed microbeads at oblique angles. As such, the Pt is subsequently coated only on one side of the arms at no angle, which offers the asymmetric placement of the catalyst critical for propulsion, as shown in Figure 11F [13]. With substrate rotation and oblique vapor direction, the coating layer can cover a much bigger area of the sphere templates than that by using conventional vapor deposition. A bubble-propelled Pt-Ag-Au shell micromotor with a smaller opening was synthesized by GALD and subsequent wet chemical etching, as shown in Figure 11G [30].
By combining an engineered strain gradient with the coated thin membranes, the membranes are able to roll into the required shapes when detached from the substrate. The rolled-up nanotechnology pioneered by Schmidt and co-workers applies strain engineering to form micro-/nanotubes from deposited thin films. A prestressed nanomembrane is coated onto a photoresist sacrificial layer patterned by photolithography, which is able to be alternatively etched by acetone. GLAD deposition is applied to guarantee accurate positioning and tube integration on a single chip. A proper control of the deposition rate and the substrate temperature, as well as the stress evolution during coating, creates the strain gradient desired for the rolling process.
The coated nanomembrane forms into a microtube once detached from the substrate by the dissolution of the sacrificial layer, as shown in Figure 12A [31, 32]. To avoid collapse of the rolled-up nanomembranes, the critical drying point is required to dry the synthesized microtubes. Microtubes with distinct opening diameters varying from 1 to 30 μm can be synthesized by modulating the built-in strain and the thickness of the nanomembranes. The lengths of the microtubes are in the range of scores of micrometers. Catalysts such as Pt consist of the inner wall of the microtubes by simply being coated onto the top layer of the nanomembranes. The wrinkle orientation of the detached membranes is defined by the different etching rates along the crystal axis and the crystal structure of the sacrificial layer.
Rolled-up nanotech. (A) Rolling-up of nanomembranes patterned with photoresist: (a, b) schematic illustration of a rolled-up microtube comprising of Pt/Au/Fe/Ti multilayers on a sacrificial photoresist layer and an array of rolled-up microtubes, respectively; (c) SEM image of a rolled-up microtube. (B) Rolled-up microtubes with GO as an outside layer. (C) Reversible rolling and unrolling of thermoresponsive polymeric Pt microtubes. (D) Particle-aided rolling process of nanomembrane upon a thermal dewetting treatment. Copyright 2009, Wiley Online Library. Copyright 2010, Wiley Online Library. Copyright 2012, ACS Publications. Copyright 2014, Wiley Online Library. Copyright 2013, Wiley Online Library.
Due to the high cost and the complex fabrication procedures of the rolled-up technique, considerable efforts have been devoted to simplifying the rolled-up procedures and decreasing its cost. Microtubes with outer layers of graphene oxide (GO) were synthesized by coating metal layers on GO nanosheets, as shown in Figure 12B [33]. Microscrolls with GO on the outer side and Pt at the inner surface were spontaneously synthesized upon sonication, resulting from material strain and weak bonding between GO layers. The diameter can be changed by modulating the thickness of the coated metal layers. A similar fabrication process of tubular microengines was demonstrated using accessible and low-cost fruit cells as support for the metallic layers. The tissue-based microengines can demonstrate extremely efficient bubble motion in the presence of H2O2. Zhao and his colleagues reported the synthesis of Pt microtubes by alternative dissolution of the poly(methyl methacrylate) (PMMA) sacrificial layer beneath the sputtered Pt layer or by H2O2-assisted lift-off of the Pt layer coated directly on a glass wafer. A transmission electron microscopy (TEM) grid template was applied to synthesize microtubes with a relatively uniform size. Despite the low cost and simple methods described above provide great possibilities for large-scale yield of microtubes, a major issue of these methods is the lack of morphology and accurate control of the size of the rolled-up microtubes. On the premise of simplifying the processes, future efforts should be devoted to the better manipulation of the rolled-up technique.
Magdanz and his colleagues reported a flexible thermoresponsive polymeric microjet resulting from the reversible folding/unfolding of the polymer at decreased and elevated temperatures (Figure 12C) [34]. Cooling of the Pt/polymer layers results in folding of the films and synthesis of microtubes in diameter 30 μm with a Pt inner layer as a catalyst, while warming leads to the unfolding of the microtubes. Hence, the rolling and unrolling procedures of the microtubes could be conducted reversibly by changing the temperature of the solution to start and stop the propulsion of the microtubes. The diameters of the microtubes synthesized by the rolled-up nanotech are all in the range of microscale.
Li and his partners took advantage of the surface tension of nanodroplets as well as the intrinsic strain relaxation in the nanomembranes to reduce the diameters of the rolled-up tubes to hundreds of nanometers. A layer of Pt was coated onto a prestrained bilayer of SiO2/TiO2 or Si/Cr on a sacrificial PMMA layer, as shown in Figure 12D [35]. In this treatment, rapid thermal process (RTP) was applied to stretch the Pt layer to the isolated islands and the nanodroplets brought considerable surface tension for rolling. On the other hand, the removal of PMMA resulted in the detachment of the nanomembranes. The synthesized microtubes exhibit higher velocities compared with those with a smoother Pt surface.
The aforementioned fabrication methods: template-assisted electrochemical deposition, PVD, and rolled-up nanotech, are effective approaches for synthesizing micro-/nanomotors. However, to achieve more complex structures, the assembly technique must be developed. The construction of devices with multiple individual tiny parts is an extremely challenging task. The assembling approach plays an essential role in micro-/nanofabrication. It is a technique that combines miniaturized components to form a required device. The unique properties of the assembling make it applicable for the synthesis of micro-/nanomotors. Not only employing self-assembling of materials to synthesize the required devices, but also the desired elements can be embedded into micro-/nanomotors by incorporating them into materials as well.
Layer-by-layer (LbL) self-assembling is a nanofabrication strategy for multilayer formation by coating selective layers of oppositely charged materials. It is an easy-operation and low-cost process, which can encapsulate diverse materials, such as tiny inorganic compounds, colloids, macromolecules, and organic molecules together. The LbL process can be applicable for a wide range of solvent-accessible surfaces, allowing the application of different templates. Encapsulation of Pt nanoparticles enables the movement of the assembled multilayer structure to be driven in H2O2 solution. Taking advantages of simplicity, versatility, and low cost, the LbL assembling, primarily employing the electrostatic interaction between oppositely charged species, has been widely employed to synthesize various multilayer materials.
He’s group firstly reported the combination of a colloid template-assisted LbL assembling with a microcontact printing method to synthesize platinum nanoparticles (Pt NPs) asymmetrically coated autonomous Janus micromotors, as shown in Figure 13A [36]. The SiO2 particles as templates were selectively dispersed into positively charged polyallylamine hydrochloride (PAH) solution and negatively charged polystyrene sulfonate (PSS) solution to form one polyelectrolyte bilayer. After five bilayers were coated, the formed particles were spread onto a glass wafer to form a monolayer that was then printed with a PDMS stamp loaded with a drop of dendritic Pt NPs suspension. The Pt NPs partially loaded hollow Janus micromotors were collected after the removal of the templates by using hydrofluoric (HF) acid. Polymer stomatocytes that are able to entrap Pt NPs into their nanocavities were reported by Wilson and collaborators, as shown in Figure 13B [37]. This approach applied the controlled transformation of spherical polymersomes into stomatocyte structures. Entrapment of the Pt NPs was achieved by adding nanoparticles to solvent-swollen polymersomes during the transformation process. H2O2 can get in touch with the catalytic Pt NPs by controlling the entrance of the stomatocytes to produce driving force for the directional motion of the stomatocytes.
Schematic diagram of various types of controllable self-assembled micro-/nanomotors. (A) Synthesis process of Pt NPs-functionalized Janus capsule motors. (B) Selective and controlled encapsulation of Pt NPs inside artificial stomatocytes during shape transformation. Copyright 2012, ACS Publications. Copyright 2012, Nature Publishing group.
The control of micro-/nanomotors is essential to meet various requirements in practical applications. The precise propulsion control of micro-/nanomotors is leading to advances in practical applications, and thus it is quite critical to put forward the controlling strategies for micro-/nanomotors. In the past years, scientists have realized the propulsion control of micro-/nanomotors by using different methods as reported below.
External magnetic field is the most common control source employed to direct and guide the micro-/nanomotors. The predetermined trajectory of micro-/nanomotors can be realized by incorporating a paramagnetic or ferromagnetic part that can be magnetized by the magnetic field. Relying on the shapes of micro-/nanomotors, the magnetic part can be introduced by either electrodeposition or PVD. The appropriately used magnetic material candidates in micro-/nanomotors are nickel (Ni) and iron (Fe).
Wang et al. reported a multifunctional nanomotor with three segments (Au-Ni-Au), which was thrust by ultrasound and steered by the magnetic field. A concavity was also decorated at the end of the Au segment by the sphere lithography process to realize asymmetric geometry. The interaction between the magnetic field and the middle magnetic Ni segment produced a predefined and controllable movement of the nanomotor. The Ni segment was used to load and deliver magnetic particles along a predetermined route as well, as shown in Figure 14A [38].
Micro-/nanomotors controlled by the magnetic field. (A) Schematic diagram of an Au–Ni–Au metal alloy propelled by ultrasound and steered by the magnetic field. (B) Magnetically steered movement of Janus capsule motors toward targeted HeLa cell sheets. (C) SEM image of Pt/Ni/Au/Ni/Au nanowire. (D) SEM/energy-dispersive X-ray (EDX) elemental analysis of Au/Ni/Pt nanotube. (E) Scheme representing the magnetic steering of Janus micromotors. (F) Remote control of micro/nanojets by magnetic field. Copyright 2013, ACS Publications. Copyright 2014, ACS Publications. Copyright 2005, Wiley Online Library. Copyright 2013, ACS Publications. Copyright 2012, ACS Publications. Copyright 2013, AIP Publications.
Magnetic orientation has proved to be extremely effective for achieving the required directionality of the self-assembled motors. Sputtering a layer of magnetic material on one side of the motors is widely applied in Janus capsule motors. The catalase-functionalized Janus capsule motor was coated with a layer of 5-nm-thick Ni before the deposition of Au. Such biocatalytic Janus capsule motors were capable of swimming in cellular media in the presence of H2O2 fuel and were steered by the applied magnetic field toward the targeted HeLa cells, as shown in Figure 14B [39]. It should be mentioned that the magnetic field is exclusively employed to steer the propulsion directionality of motors and is not strong enough to initiate the propulsion of motors by magnetic attraction.
For electrodeposited nanowire/-rod and micro-/nanotube, a Ni part can be incorporated into the structure by using electrodeposition. A self-propelled segmented Pt/Ni/Au/Ni/Au nanowire was taken as one of the earliest examples, as shown in Figure 14C [40]. The nanowire was magnetized transversely rather than longitudinally, resulting from the scale of the electrodeposited Ni part was smaller than the diameter of the wire. Magnetized nanowire can orient its net magnetic moment parallel to an external magnetic field, resulting in precise steering by manipulating the orientation of the magnetic field. Experimental results proved that the magnetic field could only direct the nanowires without changing their speed. The steered propulsion of self-propelled Au/Ni/Au/Pt-CNT nanorod as well as the delivery of magnetic microbead cargoes by it in microchannel networks was reported by Burdick et al. [20].
Magnetic steering of the electrodeposited microtube could also be achieved by additional electro-deposition of Ni. For conical microtube, Ni is grown to cover the whole inner surface of the microtube before electrodeposition of Pt, resulting in the microtube is magnetized along the tube axis. A simplified Ni/Pt alloy inner layer obtained by the co-deposition of a Ni/Pt layer can display both magnetic and catalytic properties. Unfortunately, the speed of microtube with a simplified Ni/Pt alloy inner layer in diluted H2O2 is hugely decreased because of the reduced catalytic area. For striped nanotube with different elements placed longitudinally, it can also be magnetized longitudinally due to the Ni portion has a larger dimension along the axis of the tube, demonstrating behavior similar to that of magnetotactic bacteria, as shown in Figure 14D [41].
Regarding rolled-up microtube, an additional Fe layer can be integrated into the microtube during the deposition process to realize the magnetic control. The longitudinally magnetized rolled-up microtube can monitor the direction of an external field and orient itself accordingly. A magnetized Fe-contained microtube was studied to be able to selectively pick up and deliver paramagnetic beads in the absence of an external magnetic field. The ability of a Pt Janus particle to deliver cargo has been reported by Sanchez and fellows. To realize the better control of the propulsion of catalytic Janus motors and the cargo delivery process, magnetic caps consisting of (Co/Pt) multilayers were incorporated into the structure by PVD. The magnetic caps were envisioned to align the magnetic moment along the main symmetric axis of the cap, enabling direct manipulation of the Janus motor as well as superparamagnetic cargoes delivery by using an external magnetic field, as shown in Figure 14E [42]. Precise control of magnetic Janus particles is further reported by sorting beads between the channels in microchip devices.
The individual control of microjet in a closed-loop manner and 3D propulsion control were the next steps to be considered. Recently, Misra’s and Sanchez’s research groups presented the accurately closed-loop control of microjet [43]. The authors reported precisely point-to-point closed-loop control by applying weak magnetic fields (2 mT). Another study demonstrated precise control when a flow was employed against and along the propulsion direction of the microjet. An electromagnetic setup consisting of two sets of orthogonal arrays of electromagnetic coils with a Fe core in conjunction with two microscopic systems was employed to guide the movement of microjet in 3D space, as shown in Figure 14F [43]. Microjet overcomes vertical forces, such as vertical flow buoyancy forces, and interaction forces with O2 bubbles, and thus it is able to drive downwards and swim upwards relative to reference positions.
Ultrasound not only provides energy for the motion of micro-/nanomotors but also offers an alternative manner for controlling self-propelled motors. Using ultrasound to guide micro-/nanomotors and as rapid “stop/go” switching of micro-/nanomotors in respond to “on/off” of ultrasound are investigated.
The movement direction of nanomotors can be reversed by varying the power of the ultrasound field. Fast and reversible transitions between aggregated and free-moving states of nanomotors in H2O2 were obtained in response to switching between on and off ultrasound states, as shown in Figure 15A [44]. The generation of bubbles can be disrupted by the ultrasound field. Wang et al. demonstrated the reversible control of the propulsion of PEDOT/Ni/Pt microengines by changing the applied voltage of the external transducer which produces the ultrasound field. The authors demonstrated extremely fast changes (< 0.1 s) in the motor speed and reproducible “on/off” activations that were faster than those by using other reported methods for stopping the propulsion of microjets, as shown in Figure 15B [45].
(A) Scheme representing controlling of acoustically propelled nanowire toward a HeLa cell. (B) Scheme representing ultrasound-modulated bubble propulsion of chemically powered microtubes. Copyright 2013, ACS Publications. Copyright 2014, ACS Publications.
Metallic micro-/nanomotors can perform controllable rotation resulting from rotational torque in an electric field provided by applying AC voltages to multiple electrodes, as shown in Figure 16A [46]. In addition, by applying AC electric fields to strategically designed microelectrodes, the propulsion of metallic micro-/nanomotors could be tuned by dielectrophoretic force. They could be driven to chain, accelerate and align in certain directions, as well as to disperse, concentrate and assemble into complex scaffolds, as shown in Figure 16B.
Rotation of micro/nanomotors by applying AC voltages to multiple electrodes: (A) schematic diagram of experimental setup of quadruple electrodes and (B) images of one end fixed (left) and free (right) rotating Au nanowires, respectively. Copyright 2005, APS Publications.
Using the light to guide the movement of micro-/nanomotors was also reported. For example, Solovev and collaborators studied the control of microjets by using a white light source, as shown in Figure 17A [47]. This process was mediated through the illumination of the fuel solution above Pt-patterned Si surfaces, which generates a local decrease of the surfactant and H2O2 concentration. Although white light could be applied to switch off the motion of the microjets, shorter wavelengths were attributed to suppress the production of microbubbles faster than longer wavelengths. The phenomenon can be reversible, and thus a nonactive microjet is triggered by dimming the light source. Nevertheless, the “on/off” process is not immediate since it demands a few seconds to completely terminate or to reach a constantly maximum speed.
(A) Microengine’s propulsion controlled by light. (B) NIR light-switchable motion of NIR propelled polymer multilayer rockets. Copyright 2011, Wiley Online Library. Copyright 2010, Wiley Online Library.
He and his colleagues recently reported the near infrared (NIR) light-switching “on/off” propulsion of Au nanoshell-functionalized polymer multilayer rockets, as shown in Figure 17B [48]. NIR light irradiation could rapidly generate a thermal gradient that enables reversible movement of the Au nanoshell-functionalized polymer multilayer rockets. The rockets exhibit “on/off/on” cycles in response to an adjustable NIR irradiation, along with “go/stop/go” motions. The directional movements of the rockets were terminated as the NIR irradiation is “off” and were resumed upon switching on the NIR light. Accounting for the straight propulsion behavior of NIR-propelled polymer multilayer rockets, the “on/off” NIR switching realizes the precisely predefined route of the polymer multilayer rockets. In addition, the rockets were sustained with negligible damage under 30 times of NIR irradiation and were highly durable.
Thermal control of the propulsion of artificial micro-/nanomotors has proved to be applicable for both micro-/nanowires and microtubes. The speed of Pt-Au nanowires was substantially increased upon exposure to elevated temperatures. Similar phenomenon was discovered for bubble-propelled microtubes, which has been used to compensate the effect of decreasing the fuel level.
The temperature of the solution could be controlled by two Peltier elements in connection with a direct current (DC) power supply placed below the sample containing microjets. By heating up the system to a physiological temperature, microjets increase their efficiency and are propelled at extremely low concentrations of H2O2, as shown in Figure 18 [49, 50]. In addition, soft micromotors consisted of flexible thermo-responsive polymeric microjets could reversibly fold and unfold in an accurate manner resulted from the temperature change of the solution in which they are dispersed, thereby allowing them to rapidly initiate and terminate multiple times in response to the radius of curvature accordingly. The employment of stimuli-responsive materials would be ideal for the future designs of smart micro-/nanomotors.
Micro/nanojet’s propulsion controlled by temperature. Copyright 2011, ACS Publications. Copyright 2013, RSC Publications.
The propulsion of self-propelled micro-/nanomotors could be adjusted by tuning the fuel level or chemical stimuli. In the presence of fuel concentration gradient, micro-/nanomotors can drive themselves along the gradient toward a region with a higher fuel concentration. As such, monitoring the fuel concentration and distribution can be used to direct and modulate the propulsion of micro-/nanomotors. In addition to fuel concentration, the propulsion of micro-/nanomotors is influenced by the presence of certain other chemicals. For instance, the movement of Au/Pt nanomotors was reported to be extremely accelerated upon the addition of Ag ion because of the under-potential deposition of Ag on the nanomotors, which introduces differences in surface and catalytic properties. Hydrazine (N2H4) is another chemical stimulus observed to be effective to accelerate the propulsion of Au/Pt-CNT nanomotors. For bubble-propelled micro-/nanomotors, surfactants are significantly critical to the mobility of motors, resulting from they can stimulate bubble production and detachment.
Solovev et al. reported that the production of large microbubbles from small ensembles of microjets generated a chemophoretic attraction force and a capillary force that pulled other microjets into the swarm. A more complicated experiment was demonstrated by Baraban et al., who reported a controllable manner to study the chemotactic behavior of Janus motors and tubular microjets in microfluidic channels. Both types of motors move toward the gradient of the fuel without the influence of capillary forces, as shown in Figure 19 [51].
Micro/nanomotor’s motion controlled by chemical gradient in microfluidic channel. Copyright 2013, Wiley Online Library.
There are many current and potential applications, resulting from the great advances in cargo-towing force, propulsion control, and lifetime of synthetic micro-/nanomotors. The wide range of potential applications of micro-/nanomotors covering different fields requires specific functionalization strategies in each kind of application. Herein, the functionalization of micro-/nanomotors for four main categories of applications is reported as follows: cargo delivery, environmental remediation, chemical sensors, and biomedical applications.
Cargo delivery is one of the most important envisioned applications of micro-/nanomotors. Relying on the properties of cargoes, tailored methods are desired for their corresponding delivery. A general process of how to synthesize micro-/nanomotors and employ them to deliver cargo molecules has been shown in Figure 20 [4].
Electrodeposited aptamer-functionalized micro/nanomotors for selective loading, deliver, and unloading of a protein cargo. Copyright 2009, ACS Publications.
For the cargo delivery by micro-/nanomotors, the cargo could simply be connected to the motors by magnetic attraction. The delivery of drug-loaded magnetic poly(D,L-lactic-co-glycolic acid) (PLGA) microparticles has been studied by both chemically propelled, as shown in Figure 21A [52, 53, 54], and magnetically driven micro-/nanomotors. For charged cargoes, electrostatic interaction between cargoes and micro-/nanomotors could be applied for the pick-up process. A common scheme introducing charged portions into micro-/nanomotors is to incorporate a negatively charged polymer part. Sen et al. reported that a PPy part was incorporated to a nanowire via electropolymerization, which could be attached to oppositely charged polystyrene amidine cargo via electrostatic interaction, as shown in Figure 21A. A photo-chemically triggered cargo unloading manner was proposed for cargoes loaded nanowires via electrostatic interaction. An additional Ag portion in a nanowire will be dissolved rapidly in the presence of H2O2, chloride ions (Cl−), and ultraviolet (UV) light, resulting in releasing of the cargo.
(A) Examples of the delivery of cargo using solid micro/nanorods: (a) cargo pick-up, (b) cargo delivery, and (c) cargo release, respectively. (B) Synthesis procedures for Janus spherical micro/nanomotors, drug picking-up, lipid bilayer functionalization, and drug unloading (DOX = doxorubicin hydrochloride). (C) Selective binding and delivery of biological analytes and cells by functionalized microjets. (D) Direct optical visualization of pick-up, transportation, and delivery of E. coli bacteria and polymeric drug-carrier spheres. (E) In-chip immunoassays for in situ picking up and delivery of target proteins. (F) Selective recognition of monosaccharides for loading and unloading of yeast cells. Copyright 2008, ACS Publications. Copyright 2010, Wiley Online Library. Copyright 2010, Wiley Online Library. Copyright 2014, Wiley Online Library. Copyright 2011, RSC Publications. Copyright 2012, ACS Publications. Copyright 2013, RSC Publications. Copyright 2012, ACS Publications.
Garcia-Gradilla and colleagues demonstrated that the incorporation of a negatively charged polypyrrole polystyrene sulfonate (PPyPSS) portion with an ultrasound-propelled nanowire could be served as a pH-sensitive carrier for positively charged drugs via electrostatic interaction. The unloading of the drugs was theoretically realized by a protonated PPyPSS portion in an acidic environment. The same group also reported drug-loaded nanowires depending on a nanoporous Au portion with a large surface area. Such a nanoporous device is synthesized by dealloying the Ag portion of an Au/Ag alloy grown by the coelectrodeposition of Au and Ag. The picking up of the drug doxorubicin in the nanopores via electrostatic interactions with the polymeric coating of the nanowire motors and NIR light-stimulated drop off were reported as well.
Xuan et al. reported the fabrication of self-propelled Janus nanomotors in a diameter of 75 nm. The steps are illustrated in Figure 21B [55]. Spherical mesoporous SiO2 nanoparticles (MSNs) were fabricated by using a base-catalyzed sol–gel method. Afterwards, MSNs were dispersed on an Si substrate to form a monolayer and subsequently deposited with evaporated Cr (chromium) and Pt. A brief sonication resulted in the Janus MSNs becoming spread in a solution of the anticancer drug doxorubicin hydrochloride to pick up the cargo, and subsequently mixing with 1-mg mL−1 egg phosphatidylcholine containing 1% folic acid resulted in encapsulation.
The Wang’s group reported a great capability of microtubular motors for the selective loading, delivery, and isolation of distinct target analytes of biological relevance. They bio-functionalized the outer walls of microtubes with antibodies, aptamers, lectin receptors, and ss-DNA, and thus the isolation modes of cancer cells, bacteria, proteins, and nucleic acids could be demonstrated in Figure 21C [56]. The authors made use of rolled-up microtubes with Au layers for thiol modification and template-assisted microjets with polymer walls.
Campuzano and his colleagues functionalized Au/Ni/PANI/Pt micromotors with concanavalin A (ConA) to enable selective loading of pathogenic bacteria from fuel-enhanced real samples, as shown in Figure 21D [57]. The loading, transport, and unloading events were observed by optical microscopy. The delivery of pathogenic bacteria by magnetic polymeric drug carriers could represent the basis of an attractive propulsion-based theranostics scheme. In related work, the same group later functionalized artificial catalytic micromotors with antibodies to enable in-chip immunoassays, as shown in Figure 21E [58]. Kuralay et al. fabricated poly(3-aminophenylboronic acid) (PAPBA)/Ni/Pt tubular micromotors that selectively recognize monosaccharides, which were capable of loading and drop off of yeast cells, as shown in Figure 21F [59].
One of the primary environmental applications of micro-/nanomotors is to adsorb the pollutants in water. Remediation agents could be incorporated with micro-/nanomotors as the outer surface to contribute to the purification process during propulsion. Soler et al. studied the application of microtube motors decorated with a Fe outer surface to degrade organic contaminants in water via the Fenton oxidation, as shown in Figure 22A [60]. Wang et al. reported the application of PEDOT/Pt microtubular motors to promote the degradation of chemical threats, as shown in Figure 22B [61]. In brief, the oxidation of an organophosphate nerve agent by H2O2 was enhanced in the presence of the self-propelled micromotors, which resulted in an efficient mixing of the treated aqueous solution without the aid of external mechanical stirrers.
(A) Organic pollutants degraded by multifunctional Fe/Pt micromotors in H2O2 solutions. (B) Accelerated oxidation of organophospate nerve agents by using micromotors as active mixers. (C) Loading of oil droplets by alkanethiol-modified microtubes. (D) Picking up and loading of oil, enabled by a superhydrophobic-modified outer layer. Copyright 2013, ACS Publications. Copyright 2013, Wiley Online Library. Copyright 2012, ACS Publications.
Surface modifications of micro-/nanomotors with a hydrophobic layer could also activate them to load oil droplets. Guix et al. demonstrated that the functionalized Au/Ni/PEDOT/Pt microtubes with a self-assembled monolayer (SAM) of alkanethiols on the Au outer surface could pick up and deliver oil droplets resulting from strong interactions between them, as shown in Figure 22C [62]. The same group also incorporated the rough external Au layer of microengines with long chains of self-assembled monolayers to create a super-hydrophobic absorbent layer for oil loading, as shown in Figure 22D [62].
The application of micro-/nanomotors as chemical sensors is based on the case that the propulsion speed of micro-/nanomotors can be converted into an analytically useful signal. The interaction of certain compounds in the sample with the catalytic sites of micro-/nanomotors leads to the alteration of their propulsion speed and is related to the concentration of an analyte in solution, as shown in Figure 23 [63, 64, 65, 66]. Although the field is still in its infancy, micro-/nanomotors as chemical sensors could have a number of advantages over conventional either optical or electrochemical sensors, such as sensitivity, selectivity, immunity to electrical interferences, operation in a wireless manner, and only requiring a minute amount of sample. In the past few years, some research groups demonstrated the ability of micro-/nanomotors to detect inorganic electrolytes present in blood, heavy metals, organic compounds such as dimethyl sulfoxide (Figure 23A) [63], uric acid, blood proteins such as bovine serum albumin (BSA), glucose oxidase enzymes and g-globulin, amino acids containing thiol groups, for instance, methionine, cysteine, and serine (Figure 23D) [65], peptides such as glutathione, and DNA (Figure 23A).
(A) Detection of Ag-tagged nucleic acid, which alters the propulsion of the micro-/nanomotors. (B) Antibody-decorated micromotor for protein detection. (C) Micromotor-based multiplexed immunoassay via different microscopic tracers. (D) Effect of the concentration of DMSO (dimethyl sulfoxide), cysteine, and serine on the swimming speeds of the microtubular motors. (E) Microarray immunoassay assisted by microengines. Copyright 2013, ACS Publications. Copyright 2012, ACS Publications. Copyright 2014, RSC Publications. Copyright 2013, RSC Publications. Copyright 2014, Wiley Online Library.
García and his colleagues demonstrated the first antibody-loaded tubular microengines, which were developed to load and deliver target molecules between different microfluidic chambers. Catalytic polymer/Ni/Pt microengines were bio-functionalized with antibodies targeting Immunoglobulin G (IgG) protein molecule, as a model protein, in order to realize a micromotor-based immunoassay providing “on-the-fly” loading and isolation/sorting capabilities, as shown in Figure 23B [57]. The immunocomplex could be simply observed by optical microscope through using an antigen/antibody labeled with a polymeric sphere tracer. This innovative work is highly selective and excludes time-consuming washing steps, accelerating and simplifying the general immunoassay procedures. Taking advantage of these features, Yu et al. employed antibody-loaded AuNP/PANI/Pt micromotors to exhibit rapid “on-the-fly” sandwich immunocomplexes targeting carcinoembryonic antigen. The operation takes 5 minutes with a measuring threshold of 1–1000 ng mL−1. In addition, labeling the loaded proteins with microscopic particles demonstrating different sizes and shapes facilitates the multiplexed analysis of proteins, as proved by Vilela and his colleagues (Figure 23C) [64]. In addition, the aforementioned vortex effect generated by the propulsion of micromotors can boost the mass transfer of the target toward the functionalized microjet surface (i.e. “on-the-fly”) as well as assist the mass transfer of the target molecule within the matrix of a sample solution toward a sensing surface, where the bio-receptor is situated and the target is expected to be selectively attached, as shown in Figure 23E [66].
The pioneering micro-/nanomotors offer considerable promise for biomedical applications, as shown in Figure 24 [67]. Herein, we outline some important advances of micro-/nanomotors in the biomedical field.
Categories of biomedical applications of micro/nanomotors, including sensing and isolation, drug delivery, nanosurgery, biomedical imaging. Copyright 2014, RSC Publications.
Micro-/nanojets have proven to be capable of drilling into biomaterials and soft tissues. Rolled-up thin nanomembranes can asymmetrically result in sharp edges being engineered. Nanojets were self-propelled and externally directed toward immobilized cancer cells and embedded in their interior, as shown in Figure 25A [68]. However, the toxicity of the H2O2 fuel used for the movement leads to the cells undergoing apoptosis after short periods. Therefore, other environmentally friendly sources of movement are urgently required to replace H2O2. Magnetic trigger can be used as an alternative to the motion. Conical microtubes powered by an external rotating magnetic field were placed onto liver tissue and drilled into it for long periods, as shown in Figure 25B [69]. After releasing the microtube from the biomaterial, a micrometer-sized hole was observed by SEM, as shown in Figure 25C [69]. Ultrasonic waves can also generate the propulsion of micro-/nanomotors, as shown in Figure 25D and E) [70, 71]. Bio-functionalized nanowires propelled by ultrasound have been applied for bio-sensing, and the first results of magnetic steering toward cells have been studied. Mallouk et al. demonstrated the internalization of a nanowire-based motor inside living cells, as shown in Figure 25D. Developing biocompatible materials and fuels for artificial micro-/nanomotors or the use of noninvasive external triggered motors may pave the way for biomedical applications of micro-/nanomotors in the near future [72, 73, 74, 75, 76, 77, 78, 79, 80].
(A) A catalytic nanojet drilling into an immobilized cancer cell. (B) SEM image of a magnetic microtube drilling into pig liver tissue. (C) Hole after removing the microtube. (D) Nanorods inside living HeLa cells: (a) multiple nanorods inside a HeLa cell, (b) subcellular structures (a few indicated by arrows) interacting with active acoustic motors inside a HeLa cell, and (c) two vesicular structures in a HeLa cell containing many active but crowded acoustic motors, respectively, can be seen. (E) Preparation and propulsion of perfluorocarbon-loaded microbullets (a), Computer-created diagram (b), and images of a microbullet penetrating a tissue after an ultrasound pulse (c and d), respectively. Copyright 2012, ACS Publications. Copyright 2013, RSC Publications. Copyright 2014, Wiley Online Library. Copyright 2012, Wiley Online Library.
In this chapter, the previously reported Pt-based micro-/nanomotors are presented. In detail, the propulsion mechanisms, fabrication methods, propulsion controlling methods, and applications of these synthetic micro-/nanomotors developed in the past years are summarized accordingly. Despite the rapid and significant advances in micro-/nanomotors, challenges such as specifically practical applications and smart controlling still remain to be resolved. In addition, advanced structure design and fabrication methods are demanded.
This work was supported by Ministry of Education, Singapore, under “MOE 2011-T2-2-156, ARC 18/12” program.
There are no conflicts of interest to declare.
Current agricultural and agro-industrial systems apply the linear mode of production and, therefore, the majority of today agricultural and agro-industrial production and consumption systems are unsustainable. In other words, current agricultural and agro-industrial systems are economically, environmentally, and socially not sustainable. Precisely, the problems associated with nowadays agricultural, and agro-industries are (1) inefficient use of resources, (2) inefficient use of energy, (3) high production costs, (4) high environmental risks, and (5) massive wealth gap between the poor and the rich. Therefore, sustainability is a key issue in this context, where sustainable development encompasses the integration of social and environmental issues with economic development to convene the pressing needs of the population at present without undercutting the requirements of future generations. One key issue is to mimic the sustainable models provided by natural ecosystems. Precisely, turning the linear mode of production (linear economy) into the cyclic mode of production (circular economy). The current farming and agro-industrial processes have two main problems, which are the inefficient use of energy and wastes are not utilized within the production processes, which leads to the degradation of the surrounding environment. In contrast, natural ecosystem -which should be mimicked- allows the efficient use of energy, and all wastes are bioremediated and utilized by the system. Hence, the current farming and agro-industrial processes (linear) should be amended to mimic the natural ecosystem (circular), where this leads to the concept of industrial ecology, which fills the gap between the farming and agro-industrial processes on the one hand, and the ecologically sustainable natural system on the other hand.
According to the EU, “the bioeconomy encompasses the production of renewable biological resources and the conversion of these resources and waste streams into value-added products, such as food, feed, bio-based products, and bioenergy” [1]. Furthermore, “the transition to a more circular economy, where the value of products, materials, and resources is maintained in the economy for as long as possible, and the generation of waste minimized, is an essential contribution to the EU’s efforts to develop a sustainable, low carbon, resource-efficient, and competitive economy. Such transition is the opportunity to transform the economy and generate new and sustainable competitive advantages” [2]. Consequently, the bioeconomy is broader and deeper than a circular economy. On the other hand, biomass is defined as “the biodegradable fraction of products, waste, and residues from biological origin from agriculture (including vegetal and animal substances), forestry and related industries including fisheries and aquaculture, as well as the biodegradable fraction of industrial and municipal waste” [3]. In other words, biomass types are agricultural biomass (crops residues and animal wastes), fisheries biomass, algae biomass, and forest biomass.
Circular bio-based economy aims at reaching a net zero-carbon community by creating sustainable technologies and efficient resource use approaches to substitute the fossil-based economy. The circular bioeconomy primarily depends on biomass as a building block, while social, economic, and environmental are the principal factors. The technologies that are projected to be industrialized under circular bioeconomy must guarantee that the value of product carbon is preserved to decrease the wastewater production, greenhouse gas (GHG) emissions, and impairment to the ecosystems. In the context of circular bioeconomy growth, the biomass production, process advancements, and reuse approaches ought to be well defined to meet the global supply chain and demand. This urges conducting techno-economic assessment (TEA) and life cycle analysis (LCA) of every product and process.
Bioproducts or bio-based products are biomaterials, biochemicals, and bioenergy derived from renewable biological resources. The biological resources include agriculture, forestry, and biologically derived waste. One of the renewable bioresources is lignocellulose. Cellulose-based materials and lignocellulosic tissues are biologically derived natural resources.
Conventional bioproducts and emerging bioproducts are two broad categories used to categorize bioproducts. Examples of conventional bioproducts include building materials, pulp and paper, and forest products. Examples of emerging bioproducts include biofuels, bioenergy, starch-based, and cellulose-based ethanol or bioethanol, bio-based adhesives, biochemicals, bioplastics, etc. Bioproducts derived from bioresources can replace much of the fuels, chemicals, plastics, etc. that are currently derived from petroleum. As a result, the emerging bioproducts are environmentally friendly products and independent of fossil sources.
Bioprocessing and bioproducts production include the use of engineered microbiological systems for generating biofuels, bioelectricity, and new high-value bioproducts. Additionally, scientists are investigating the utilization of forestry products in untraditional applications, including industrial foams and flame-retardant materials. This needs to combine a conglomerate of mathematics, biology, and industrial design, and consists of numerous varieties of biotechnological processes, which pertain to the design, development, and implementation of processes, technologies for the sustainable manufacture of biomaterials, biochemicals, and bioenergy from renewable bioresources. Bioprocessing deals with the design and development of equipment and processes for making bioproducts such as food, feed, pharmaceuticals, nutraceuticals, biochemicals, biopolymers, and paper from biological materials (i.e., biomaterials). Practically, bioprocessing takes place in devices called bioreactors.
Bioreactors are categorized, based on the mode of operation, as a batch, semi-continuous or continuous bioreactors. Microorganisms growing in bioreactors may be submerged in a liquid medium or may be attached to the surface of a solid medium. The bioenvironmental conditions inside the bioreactor, such as temperature, nutrient concentrations, pH, and dissolved gases (especially oxygen for aerobic processes) affect the growth and productivity of the microorganisms.
Biological wastes i.e., biowastes, generated from agriculture, wastewater treatment, or industry are a largely untapped source for the production of value-added bioproducts or bioenergy. Their recovery utilizes biological and chemical processes that provide alternative sources for chemical feedstocks to produce different products e.g., bioplastics or other biopolymers, high-value biochemicals, protein for animal feed, and enzymes. For example, nutrients, cellulose, volatile fatty acids, extracellular polymeric substances, or proteins can be recovered from biowastes. Similarly, many opportunities exist for alternative energy products, e.g., bioethanol, biobutanol, biogas, biohydrogen, or bioelectricity. Resource biorecovery thus supports sustainability goals by reinjecting products into the circular economy.
For instance, the value-added bioprocessing of fish waste produces numerous bioproducts, which are: (1) pharmaceuticals such as proteins, jadomycin, collagen, lactic acid, glycerol, proteases, lipases, and collagenases; (2) nutraceuticals such as omega-3, amino acids, fish oil, fatty acids, carotenoids, isoflavones, and lutein; (3) chemicals such as 1,2-propanediol and 1,3-propanediol, dihydroxy-acetone, and methanol; (4) biofuels such as biodiesel, bioethanol, and biohydrogen; and (5) further products such as fish meal and fish silage. On the other hand, the value-added bioprocessing of slaughtering waste produces the same above-mentioned products except that the intermediate product, in this case, is the tallow compared to fish oil as an intermediate product in the bioprocessing of fish waste.
Furthermore, there are several potential uses of fish waste in the production of further pharmaceuticals such as chymotrypsin, pepsin, enzyme inhibitors, anticoagulants, insulin, nucleic acid, nucleotides, protamine, and proteolytic enzymes. Besides, several biochemicals can be produced such as bile salts, glue, gelatin, leather, and pearl essence.
The industrial ecology is the design of industrial infrastructures as a series of interlocking manufactured ecosystems in order to maximize the energy use efficiency, reduce the costs, reduce the environmental problems, identify new value-added products, and maximize the resources use efficiency, which leads to the sustainability. An important key issue is the interpretation of the insinuation of employing the ecological models to restore the agro-industrial systems, through applying the concepts of eco-design and eco-efficiency leading to a cleaner production allowing to reach a zero-waste and zero-emission system. This requires inevitably conducting environmental impact assessment and life cycle analysis of the agro-industrial processes and products. On the other hand, the aim of eco-efficiency is to boost the values of products by optimizing the utilization of resources and minimizing the negative environmental impacts by incorporating both efficiency and innovation into the industrial process without expensive pollution control techniques.
The cleaner production procedure is the first step in the implementation of the concept of industrial ecology. The procedure includes: (1) the examination of production systems in terms of the efficient use of natural resources and the efficient use of energy, and (2) the utilization of life cycle analyses method to evaluate the products and the agro-industrial processes in order to minimize waste and pollution as well as reduce costs and identify new prospects such as new products and employment opportunities.
Regarding the products, the procedure aims at reducing the negative impacts throughout the entire life cycle of the product from cradle to grave, i.e., from design to final disposal. Regarding the agro-industrial processes, cleaner production aims at (1) efficient use of raw materials, (2) efficient use of energy, and (3) reduction of emissions and wastes. An important key issue is to incorporate environmental concerns into designing processes and delivering the products.
The concept of integrated bioindustrial systems aims at (a) designing circular production and consumption systems leading to maximize the efficiencies of resources and energy uses and to allow the required energy and resources for forthcoming development, (2) forming a further ecologically sound and healthy environment through less waste is generated at each level of production and the conversion of waste into value-added products, and (3) emphasizing the socio-economic development through creating new employment opportunities and ground-breaking technologies and new products.
The biorefinery is the cornerstone of the integrated bioindustrial systems, where a biorefinery is a production plant that combines bioconversion processes biomass and devices such as bioreactors to generate biofuels, electrical energy, heat energy, and value-added biochemicals from biomass. The International Energy Agency, Bioenergy Task 42 on Biorefineries, has defined biorefining as the sustainable processing of biomass into a spectrum of bio-based products (food, feed, chemicals, materials) and bioenergy (biofuels, power, and/or heat). Considering that biomass is all organic matters -except fossil fuels- such as forest materials, agricultural crops residues, livestock manure, organic fraction of municipal solid wastes, fish processing wastes, and food processing wastes [4].
The concept of biorefinery has several objectives: (1) maximizing energy use efficiency, (2) maximizing resource use efficiency, (3) minimizing environmental problems, (4) creating new value-added products, and (5) creating new employment opportunities. However, there are some critical concerns such as the competing uses of materials, market demands, and production costs.
The biorefinery has several advantages: (1) through producing numerous products, a biorefinery takes advantage of the numerous components in biomass and their intermediates then intensifying the value derived from the biomass, and (2) through producing various low-volume, nevertheless high-value, chemical products such as nutraceuticals and pharmaceuticals and a low-value, nonetheless high-volume liquid transportation fuel such as biodiesel and bioethanol, (3) meanwhile generating electrical energy and heat, through combined heat and power (CHP) plant, and (4) creating new high value-added products maximizes the feasibility, where the high-volume fuel’s production meet the energy demands, and the electricity and heat production minimizes the energy costs and decreases the greenhouse gas (GHG) emissions.
However, the subsequent concerns should be considered: (1) risk of excessive consumption of edible crops, (2) risk of deterioration of organic and mineral content of soils, (3) risk of excessive utilization of chemical fertilizers and pesticides to advance the production levels, (4) risk of competition between food and biorefinery, and (5) risk of deforestation.
The following is an approach to transform the present agricultural systems (beef, dairy, and poultry farms as well as cereals and vegetable crops production) and agro-industrial systems (ethanol industry and fish industry) into integrated bioindustrial systems by altering their linear mode of production into a circular mode of production to create a coherent bioeconomy, where the bioeconomy includes the conversion of renewable bioresources and waste streams into value-added bioproducts, such as food, feed, pharmaceuticals, nutraceuticals, biomaterials, biochemicals, biofuels, and bioenergy.
Cereal and vegetable production encompasses the utilization of several inputs such as water, fertilizers, pesticides, seeds, and energy. The products are grains, fruits, and tuber/roots. However, the waste is agricultural crops residues (Figure 1). The concept of bioeconomy is to use the output i.e., waste, of an industry or production system as an input i.e., feedstock, in another new industry. Therefore, this waste is planned to be used as feedstock for a new forage industry, where the produced forages are used for feeding livestock in a new livestock production system that produces milk and meat. However, this industry generates animal waste i.e., manure, which is planned to be used as feedstock for a new biogas plant that produces biogas that fuels the cereal and vegetable crops production system. Besides, the generated sludge is used as a biofertilizer within the crops production system. Part of the generated sludge is used in a new compost facility and the produced compost is used within the crops production system as a biofertilizer. An important key issue is that 4 new industries were established and, therefore, 5 new products were produced, which are considered as economic development. It should be noticed that the core of all these newly planned industries and facilities, which were integrated with the crops production system, is creating new employment opportunities, which is considered as social development. Furthermore, these integrated bioindustrial systems have zero-waste, zero-emission, and efficient resources and energy use, which are considered as environmental development (Figure 2).
Linear mode of cereal and vegetable crops production (the orange oval designates the input, the blue rectangle designates the industry, the green hexagon designates the product, and the red circle designates the waste).
Cyclic mode of cereal and vegetable crops production through integrated bioindustrial systems (the orange oval designates the input, the blue rectangle designates the industry, the green hexagon designates the product, the red circle designates the waste, and the yellow wave designates the employment opportunity).
Beef and dairy production encompass the utilization of several inputs such as water, forages, and energy. The products are milk and meat. However, the wastes are slaughter waste, manure, and whey (Figure 3). The concept of bioeconomy is to use the output i.e., waste, of an industry or production system as an input i.e., feedstock, in another new industry. Therefore, the slaughter waste is used as feedstock in a biorefinery to produce biofuels, biochemicals, pharmaceuticals, and nutraceuticals. Additionally, manure and whey are planned to be used as feedstock for a new biogas plant, where the produced biogas is used for fueling the beef and dairy production system. The biogas plant generates sludge, which is used as biofertilizer for a new crops production system that produces grains and tuber/roots. Besides, the generated crop residues are used as feedstock for the forage industry, which produces forages for beef and dairy production. Part of the generated crops residues is used in a new compost facility and the produced compost is used in fertilizing the crops production as biofertilizer. An important key issue is that 5 new industries were established and, therefore, 9 new products were produced, which are considered as economic development. It should be noticed that the core of all these newly planned industries and facilities, which were integrated with the beef and dairy production system, is creating new employment opportunities, which is considered as social development. Furthermore, these integrated bioindustrial systems have zero-waste, zero-emission, and efficient resources and energy use, which are considered as environmental development (Figure 4).
Linear mode of beef and dairy production (the orange oval designates the input, the blue rectangle designates the industry, the green hexagon designates the product, and the red circle designates the waste).
Cyclic mode of beef and dairy production through integrated bioindustrial systems (the orange oval designates the input, the blue rectangle designates the industry, the green hexagon designates the product, the red circle designates the waste, and the yellow wave designates the employment opportunity).
The poultry industry encompasses the utilization of several inputs such as water, forages, and energy. The products are meat and eggs. However, the wastes are slaughter waste and manure (Figure 5). The concept of bioeconomy is to use the output i.e., waste, of an industry or production system as an input i.e., feedstock, in another new industry. Therefore, the slaughter waste is used as feedstock in a biorefinery to produce biofuels, biochemicals, pharmaceuticals, and nutraceuticals. Additionally, poultry manure is planned to be used as feedstock for a new biogas plant, where the produced biogas is used for fueling the poultry production system. The biogas plant generates sludge, which is used as biofertilizer for a new crops production system that produces grains and tuber/roots. Besides, the generated crop residues are used as feedstock for the forage industry which produces forages for the poultry farms. Part of the generated crops residues is used in a new compost facility and the produced compost is used in fertilizing the crops production as biofertilizer. An important key issue is that 5 new industries were established and, therefore, 9 new products were produced, which are considered as economic development. It should be noticed that the core of all these newly planned industries and facilities, which were integrated with the poultry production system, is creating new employment opportunities which is considered as social development. Furthermore, these integrated bioindustrial systems have zero-waste, zero-emission, and efficient resources and energy use, which are considered as environmental development (Figure 6).
Linear mode of poultry production (the orange oval designates the input, the blue rectangle designates the industry, the green hexagon designates the product, and the red circle designates the waste).
Cyclic mode of poultry production through integrated bioindustrial systems (the orange oval designates the input, the blue rectangle designates the industry, the green hexagon designates the product, the red circle designates the waste, and the yellow wave designates the employment opportunity).
The fish processing industry encompasses the utilization of several inputs such as water, feed, and energy. The product is canned fish. However, the wastes are a large amount of fish waste and a large amount of wastewater (Figure 7). The concept of bioeconomy is to use the output i.e., waste, of an industry or production system as an input i.e., feedstock, in another new industry. Therefore, a large amount of wastewater is planned to be used as feedstock for a new wastewater treatment plant, where the treated water is used as input water in the fish processing industry. Further, this plant generates sludge, which is planned to be used as feedstock for a new biogas plant that produces biogas that fuels the finish processing industry. Besides, the generated sludge is considered a new product as biofertilizer. On the other hand, the large amount of fish waste is used as feedstock for a new biorefinery that produces fish meal and fish silage, pharmaceuticals (proteins, jadomycin, collagen, lactic acid, glycerol, proteases, lipases, and collagenases), nutraceuticals (omega-3, amino acids, fish oil, fatty acids, carotenoids, isoflavones, and lutein), chemicals (1,2-propanediol and 1,3-propanediol, dihydroxy-acetone, and methanol), biofuels (biodiesel, bioethanol, and biohydrogen). An important key issue is that 6 new industries were established and, therefore, a multitude of new products were produced, which are considered as economic development. It should be noticed that the core of all these newly planned industries and facilities, which were integrated with the fish processing industry, is creating new employment opportunities, which is considered as social development. Furthermore, these integrated bioindustrial systems have zero-waste, zero-emission, and efficient resources and energy use, which are considered as environmental development (Figure 8).
Linear mode of fish industry (the orange oval designates the input, the blue rectangle designates the industry, the green hexagon designates the product, and the red circle designates the waste).
Cyclic mode of fish industry through integrated bioindustrial systems (the orange oval designates the input, the blue rectangle designates the industry, the green hexagon designates the product, the red circle designates the waste, and the yellow wave designates the employment opportunity).
The bioethanol industry encompasses the utilization of inputs such as energy and raw cellulosic materials. The product is bioethanol. However, the waste is broth (Figure 9). The concept of bioeconomy is to use the output i.e., waste, of an industry or production system as an input i.e., feedstock, in another new industry. Therefore, this waste is planned to be used as feedstock for a new processing industry that produces wastewater and biofertilizer, where these products are used in a new hydroponics system that produces biowastes (crops residues). These wastes i.e., crop residues, are planned to be used as feedstock for a new forage industry that produces forages for a new livestock production system. However, this industry generates animal waste i.e., manure, which is planned to be as feedstock for a new biogas plant, which produces biogas that fuels the bioethanol industry. Besides, the generated sludge is used as biofertilizer for a new crops production system. Part of the generated sludge is used in a new compost facility and the produced compost is used within the crops production system as biofertilizer. The produced crops residues from the new crops production system as feedstock in a new compost industry, which produces a biofertilizer. An important key issue is that 6 new industries were established and, therefore, 7 new products were produced which are considered as economic development. It should be noticed that the core of all these newly planned industries and facilities, which were integrated with the bioethanol industry, is creating new employment opportunities, which is considered as social development. Furthermore, these integrated bioindustrial systems have zero-waste, zero-emission, and efficient resources and energy use, which are considered as environmental development (Figure 10).
Linear mode of bioethanol industry (the orange oval designates the input, the blue rectangle designates the industry, the green hexagon designates the product, and the red circle designates the waste).
Cyclic mode of bioethanol industry through integrated bioindustrial systems (the orange oval designates the input, the blue rectangle designates the industry, the green hexagon designates the product, the red circle designates the waste, and the yellow wave designates the employment).
Digitalization is essential to the advancement of the bioeconomy. Digitalization is promoting intelligibility throughout the value chains and facilitates to scrutinize the conformity with afforded standards. Digitalization modifies the route for expanding traditional bioeconomy and is converting the bioeconomy into a progressively multi and interdisciplinary proficient sector.
The digital revolution in the bioeconomy has 3 unique aspects: (1) the utilization of digital tools as a tool for monitoring. For instance, real-time monitoring of farming operations such as crops, and livestock can provide timely and feasibly added value. Likewise, in forestry, monitoring provides added value by processing data, optimizing the conservation and use of forest products, (2) data aid the development of value chains in terms of reusing, recycling, and repairing. Digitalization provides data analysis for biorefineries or bioindustry can assist in identifying new products evolving from what was formerly considered as biowaste, and (3) data-driven at its core, biosciences are growing precipitously owing to the expanding repository of information. Its application can be observed through a wide range of products and services such as the usage of genomes for therapeutics, personalized medicine, and pharmaceuticals. It can be noticed as well in the advancement of biochemicals as alternatives for petrochemicals.
Digital tools offer a variety of prospects within the traditional bioeconomy sectors such as farming, fisheries, and forestry. For farmers, the ability to track and monitor their livestock and crops boosts daily operations and grants for accurate development. There are also prospects for improved precision, as data is pooled promptly throughout the value chain from forage to dairies, slaughterhouses, products manufacturing, marketing, and consumption. Within the forestry industry, digital tools can be used for monitoring, forecasting, and management of forests.
Digitalization is encouraging practices innovation by boosting both supply and value chains in the circular bio-based economy. Thus, digitalization is able to play a role as a facilitator of circular bioeconomy procedures by for instance altering business patterns. Manipulating data to detect gaps for improving manufacture, or even to pinpoint how to help obtain value from both current production lines and bio-based waste streams are components of this development. At this point, streams of the circular bio-based economy, for instance, biowaste streams, are employed in different approaches since the data-driven procedures are strengthening the bioeconomy.
Digitalization is a component of the circular bioeconomy, where the bioindustrial systems are aiming at applying the circular economy standards that broaden the lifecycle of biowaste by recycling them as feedstock for bioenergy generation. Digitalization, smart algorithms, and advanced computer modeling guarantee resource boosting in the bioindustrial systems, raise the value of green production and are a factor in energy trade-off. Applications include open innovation platforms providing data access, which is open for research and development (R&D) as well as business. Digitalization can be used to create higher-value products in the circular bio-based economy. Digital tools can be implemented for making new value-added bioproducts. For instance, the production of novel and high-value bioproducts using existing bioresources.
Big data is cornerstone in developing biosciences. In the health sector, for instance, big data is accelerating encouraging results in biomedical research. At this point, the quick leap of data-driven analysis is anticipated to reach a higher level of personalized medicine and pharmaceuticals. High levels of digitalization such as blockchain and artificial intelligence coupled with its application in, for instance, agriculture, aquaculture, and forestry, brand-new bioproducts, and recycling of by-products are projected to occur. The intersecting role of data for R&D as well as an invention in bioeconomy is applied in contemporary waste management such as the use of bacteria in biowaste degradation.
Data analysis is crucial for a profitable green transition. Numerous biorefineries implement data in fostering the applications of biosciences in utilizing, for instance, forest by-products. Biomaterials such as lignin were found to be valuable feedstock in the production of food, feed, and adhesives. Technologies such as pyrolysis use biological but inedible feedstock and produce liquid bio-oils. The bio-oil is consistent with the current fossil oil infrastructure, and thus fills one of the gaps arising between the bio-based economy and the petroleum-based economy. The rapid leap of data analysis is able to accelerate finding solutions for global challenges.
A digital transformation is in progress in the circular bio-based economy. Guaranteeing that rural communities realize the profits of this transformation necessitates a re-outlining of the discussion to emphasize not only the digitalization itself but the growth potential it offers. This prospective is comprehensive and involves the formation of innovative bioproducts, services, and bioindustries. While based on rural resources, these opportunities necessitate additional collaboration that reinforces rural–urban relationships. The digital revolution of the circular bio-based economy likewise retains the capability to carry out businesses in conventional circular bio-based economy sectors attracting a wider cross-section of communities. This leads to create new employment opportunities for rural communities.
Generally, the applications of digital tools include prototyping electronic boards, internet of things (IoT) platforms, software, and cellphone applications to control the operation of the bioproducts production systems as well as compute the input materials and energy on the one hand and the output materials and energy on the other hand. Similar applications include livestock farming, for example detecting the activity and health of the animals and informing the animal owner. Further applications include operating the cooling/heating systems based on detected indoor conditions in greenhouses and livestock barns. Another application is in precision farming to control the farming operations conducted by agricultural machinery connected to satellites. Further application is that digital tools can control the interoperability of agricultural systems e.g., control the soil-based sensors to be consistent with the tractor. Additionally, the role of mechatronics is highly foreseen in these applications. Finally, a further application is the use of QR-codes (Quick Response code) to boost comprehensibility across the value chain. For instance, QR-codes are used to track livestock, allowing consumers to trace the food they consume from its source through the route to the retailer. Several applications in this context were developed as cell phone applications [5] and desktop software [6, 7, 8, 9].
Nanotechnology and laser radiation have been implemented in the production process of several bioproducts [10, 11, 12, 13, 14, 15, 16]. Besides, the implementation of life cycle analysis (LCA) and environmental impact assessment (EIA) methodologies are of high importance to analyze the life cycle of bioproducts and to determine the environmental impact of the production processes [17, 18, 19, 20, 21]. A key issue is to conduct a techno-economic assessment (TEA) of the used technologies in the production process [22].
This study provides an approach to convert the present agricultural systems (beef, dairy, and poultry farms as well as cereals and vegetable crops production) and agro-industrial systems (ethanol industry and fish industry) into integrated bioindustrial systems and biorefineries through amending their linear mode of production into a circular mode of production to develop a sustainable bioeconomy. This development includes the bioconversion of biowaste streams from the existing agricultural and agro-industrial systems into value-added bioproducts, such as food, feed, pharmaceuticals, nutraceuticals, biomaterials, biochemicals, biofuels, and bioenergy where these novel bioproducts are considered as economic development. Whereas the core of the planned bioindustries is creating new employment opportunities, which is considered as social development. Furthermore, these integrated bioindustrial systems have zero-waste, zero-emission, and efficient resources and energy use, which are considered as environmental development. An important key issue is that digitalization guarantees resource boosting in the bioindustrial systems, where applications include the development of electronic boards, internet of things (IoT) platforms, software, and cellphone applications for monitoring and controlling the operations, computing input and output materials, and energy, and fostering comprehensibility across the value chain. Figure 11 summarizes the fields of science related to bioeconomy.
The fields of science related to bioeconomy.
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