Cover
Title Page
1. Copyright
2. Chapter 1: Change Thinking toward Nanoarchitectonics
  1. 1.1 From Nanotechnology to Nanoarchitectonics
  2. 1.2 Way of Nanoarchitectonics
  3. 1.3 Materials Nanoarchitectonics
  4. References
Part I: Zero- and One-Dimensional Nanoarchitectonics
1. Chapter 2: Architectonics in Nanoparticles
  1. 2.1 Introduction
  2. 2.2 Soft Nanoparticles
  3. 2.3 Hierarchical Architecturing of Solid Nanoparticles
  4. 2.4 Janus (Asymmetric) Nanoparticles
  5. 2.5 Functional Architectures on the Surface of Nanoparticles
  6. 2.6 Summary
  7. References
2. Chapter 3: Aspects of One-Dimensional Nanostructures: Synthesis, Characterization, and Applications
  1. 3.1 Introduction
  2. 3.2 Synthesis of NCs
  3. 3.3 Growth Mechanisms of 1D Nanocrystals
  4. 3.4 Post-Synthetic Modification
  5. 3.5 Essential Characterization Techniques
  6. 3.6 Promising Applications of 1D NCs
  7. 3.7 Summary and Conclusions
  8. References
3. Chapter 4: Tubular Nanocontainers for Drug Delivery
  1. 4.1 Introduction
  2. 4.2 Carbon Nanotubes for Drug Delivery
  3. 4.3 Halloysite-Nanotube-Based Carriers for Drug Delivery
  4. 4.4 Tubular Nanosized Drug Carriers: Uptake Mechanisms
  5. 4.5 Conclusions
  6. References
Part II: Two-Dimensional Nanoarchitectonics
1. Chapter 5: Graphene Nanotechnology
  1. 5.1 Introduction
  2. 5.2 Electronic States of Graphene
  3. 5.3 Graphene Nanoribbons and Edge States
  4. 5.4 Spintronic Properties of Graphene
  5. 5.5 Summary
  6. References
2. Chapter 6: Nanoarchitectonics of Multilayer Shells toward Biomedical Application
  1. 6.1 Introduction
  2. 6.2 Hollow-Structured Multilayers
  3. 6.3 Multilayer Shells on Template
  4. 6.4 Summary and Outlook
  5. Acknowledgments
  6. References
3. Chapter 7: Layered Nanoarchitectonics with Layer-by-Layer Assembly Strategy for Biomedical Applications
  1. 7.1 Layer-by-Layer Assembly Technique
  2. 7.2 LbL-Assembled Layer Architectures with Tunable Properties
  3. 7.3 The Application of the LbL-Assembled Layer Architectures in Biomedicine
  4. 7.4 Summary and Outlook
  5. Acknowledgment
  6. References
4. Chapter 8: Emerging 2D Materials
  1. 8.1 Introduction
  2. 8.2 Revisiting Uniqueness of Graphene as the Archetype of 2D Materials Systems
  3. 8.3 Emerging 2D Materials
  4. 8.4 Remarks
  5. Acknowledgment
  6. References
Part III: Three-Dimensional and Hierarchic Nanoarchitectonics
1. Chapter 9: Self-Assembly and Directed Assembly
  1. 9.1 Introduction
  2. 9.2 Amphiphile Self-Assembly
  3. 9.3 π-Conjugated Molecule Self-Assembly
  4. 9.4 Peptide Self-Assembly
  5. 9.5 Self-Assembly of Block Polymers
  6. 9.6 DNA-Directed Self-Assembly
  7. 9.7 Directed Self-Assembly of Nanoparticles
  8. 9.8 LB-Technique-Directed Alignment of Nanostructures
  9. 9.9 Conclusions
  10. References
2. Chapter 10: Functional Porous Materials
  1. 10.1 Introduction
  2. 10.2 Classification of Porous Materials
  3. 10.3 Functional Frameworks: from Inorganic, through Organic, to Inorganic–Organic
  4. 10.4 Summary and Outlook
  5. References
3. Chapter 11: Integrated Composites and Hybrids
  1. 11.1 3D Hybrid Nanoarchitectures Assembled from 0D and 2D Nanomaterials
  2. 11.2 3D Hybrid Nanoarchitectures Assembled from 1D and 2D Nanomaterials
  3. 11.3 3D Hybrid Nanoarchitectures Assembled from 2D and 2D Nanomaterials
  4. 11.4 Other Approaches to 3D Hybrid Nanoarchitectures
  5. 11.5 Conclusion
  6. References
4. Chapter 12: Shape-Memory Materials
  1. 12.1 Introduction
  2. 12.2 Fundamentals of Shape-Memory Effect in Polymers
  3. 12.3 Categorization of Shape-Memory Polymers on the Basis of Nanoarchitectonics
  4. 12.4 Shape-Memory Polymers with Different Architectures
  5. 12.5 New Directions in the Field of Shape-Memory Polymers
  6. 12.6 Conclusions
  7. References
Part IV: Materials Nanoarchitectonics for Application 1: Physical and Chemical
1. Chapter 13: Optically Active Organic Field-Effect Transistors
  1. 13.1 Introduction
  2. 13.2 Phototransistors
  3. 13.3 Photochromism in OFETs
  4. 13.4 Summary and Perspectives
  5. References
2. Chapter 14: Efficient Absorption of Sunlight Using Resonant Nanoparticles for Solar Heat Applications
  1. 14.1 Introduction
  2. 14.2 Electromagnetic Analysis for Finding the Resonance Conditions of Nanoparticles
  3. 14.3 Plasmon Resonance Nanoparticles for Sunlight Absorption
  4. 14.4 Mie Resonance Nanoparticles for Sunlight Absorption
  5. 14.5 Applications of Resonant Nanoparticles
  6. 14.6 Summary
  7. Acknowledgments
  8. References
3. Chapter 15: Nanoarchitectonics Approach for Sensing
  1. 15.1 Introduction
  2. 15.2 Layered Mesoporous Carbon Sensor
  3. 15.3 Layered Graphene Sensor
  4. 15.4 Hierarchic Carbon Capsule Sensor
  5. 15.5 Cage-in-Fiber Sensor
  6. 15.6 Summary
  7. References
4. Chapter 16: Self-Healing
  1. 16.1 Introduction
  2. 16.2 History of Self-Healing Materials
  3. 16.3 Dynamic Cross-links to Construct a Self-Healing Hydrogel Network
  4. 16.4 Further Applications of Self-Healing Materials
  5. 16.5 Conclusion
  6. References
Part V: Materials Nanoarchitectonics for Application 2: Biological and Biomedical
1. Chapter 17: Materials Nanoarchitectonics: Drug Delivery System
  1. 17.1 Introduction
  2. 17.2 Conclusion and Future Trends
  3. References
2. Chapter 18: Mechanobiology
  1. 18.1 Introduction
  2. 18.2 Micropatterning Cellular Shape and Cluster Geometry
  3. 18.3 Dynamic Micropatterning Single Cells and Cell Collectives
  4. 18.4 Nanopatterning Cell–Extracellular Matrix Interactions
  5. 18.5 Concluding Remarks
  6. References
3. Chapter 19: Diagnostics
  1. 19.1 Introduction
  2. 19.2 Immunoassays
  3. 19.3 Nucleic Acid Tests
  4. 19.4 Stimuli-Responsive Biomarker Separations
  5. 19.5 Stimuli-Responsive Diagnostics in the Developing World
  6. 19.6 Conclusions
  7. References
4. Chapter 20: Immunoengineering
  1. 20.1 Introduction
  2. 20.2 Immunoevasive Biomaterials
  3. 20.3 Immune-Activating Biomaterials
  4. 20.4 Immunosuppressive Biomaterials
  5. 20.5 Conclusions
  6. References
5. Index
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List of Illustrations

Chapter 1: Change Thinking toward Nanoarchitectonics
1. Figure 1.1 Fabrication characteristics at different size scales and nanoarchitectonics concept.
Chapter 2: Architectonics in Nanoparticles
1. Figure 2.1 The scheme for nanoparticles with various architectures.
2. Figure 2.2 Logic gate nanoparticles that show a dual response to reactive oxygen species (ROS) and low pH.
3. Figure 2.3 Programmable self-assembly of nucleic acid nanoparticles for targeted in vivo siRNA delivery.
4. Figure 2.4 Template-directed formation of multicompartment mesoporous silica nanoparticles with branched shapes.
5. Figure 2.5 Polymeric micelles for the synthesis of mesoporous platinum nanospheres.
6. Figure 2.6 Self-templated formation of flake-shelled silica capsule with morphology flexibility to stimuli.
7. Figure 2.7 Scalable and rapid fabrication of functionalized particles by spray-assisted layer-by-layer PRINT process.
8. Figure 2.8 Engineering homogeneous doping in upconversion nanoparticles by successive layer-by-layer process.
9. Figure 2.9 The formation of soft, nanoscale Janus particles with tunable Janus balance by triblock terpolymers.
10. Figure 2.10 Control of the surface architecture and reactivity of nanoparticles by peptidic multicoordinating ligands on surface.
Chapter 3: Aspects of One-Dimensional Nanostructures: Synthesis, Characterization, and Applications
1. Figure 3.1 (a) Band edge discretization in semiconductor NCs compared to molecules and bulk solids. (b) A scheme showing various types of electronic transition and mid-gap states of NCs and their respective roles in electron or hole recombination. (c) Size-dependent tunability of the photoluminescence color of colloidal CdSe NCs.
2. Figure 3.2 (a) TEM image of CdSe NRs with size of 4 nm × 20 nm, synthesized using organometallic method.
3. Figure 3.3 Schematic representation of anisotropic NC growth in solution with specific examples. Seed-mediated solution–liquid–solid growth: (a) schematic representation of the SLS growth processes.
4. Figure 3.4 (a) A sketch showing generic exchange of organic ligands by metal chalcogenide complexes. (b) TEM image of 8.1-nm CdSe NCs stabilized with SnTe₄⁴⁻ in DMSO. (c) Comparison of I–V characteristics for the film of dodecanethiol-capped Au NCs and Sn₂S₆⁴⁻ capped Au NCs.
5. Figure 3.5 Systematic transformation of CdS NRs into Cu₂S and then PbS NRs through cation exchange reaction. (a) TEM images of as-synthesized CdS, (b) intermediate Cu₂S, and (c) the final PbS NRs. The arrows indicate the order of cation exchange products. (d) Absorption spectra for CdS, Cu₂S, and PbS NRs. (e) XRD patterns for the corresponding NRs. The lines under the spectra are the JCPDS patterns for each material.
6. Figure 3.6 (a) HRTEM images of CdS NWs. (b) Plot of emission intensity ratio versus detection angle for the microstrings of CdS NWs formed by electric field (squares) and stirred suspension (triangles) fitted with sine function (solid curves).
7. Figure 3.7 Basic configurations of NC-based field-effect transistor (FET): (A) bottom-gated FET and (B) top-gated FET. S, D, and G are the source, drain, and gate electrodes respectively.
8. Figure 3.8 (A) Current–voltage (J–V) characteristics of a CIS NWs photovoltaic device. Inset: TEM images of CIS NWs.
9. Figure 3.9 (a) TEM image of CdSe NWs. Inset: AFM image of a network of NWs formed on a SiO₂/Si substrate. (b) I–V curve of a CdSe NW showing the current in dark and photoconductivity under illumination. (c) Currents in dark and under broadband illumination at 40 V bias as a function of temperature. The sharp thermal activation onset indicates that the thermally generated carriers across the band gap of CdSe dominate the transport properties.
10. Figure 3.10 (a) A sketch showing the free energy diagram of a chemical reaction coordinate with and without catalytic material. (b) The variation of the relative coverage N atoms (y) chemisorbed at 693 K at various Fe single-crystal surfaces with exposure to gaseous N₂.
Chapter 4: Tubular Nanocontainers for Drug Delivery
1. Figure 4.1 A sketch demonstrating a typical nanotube-based drug delivery container carrying the drug cargo inside the lumen or on the outside surface and having stimuli-responsive end stoppers.
2. Figure 4.2 Synthesis of hydrophilic multiwalled carbon nanotubes externally loaded with magnetite nanoparticles. (a) Grafting of PAA onto the carbon nanotubes via in-situ free radical polymerization; (b) Deposition of Fe₃O₄ nanoparticles on the surface via chemical co-precipitation method; (c) External loading of gemcitabine by physical adsorption.
3. Figure 4.3 Confocal images of cells after incubation in solutions of functionalized single-wall carbon nanotubes (SWCNTs) (a) after incubation in 2, (b) after incubation in a mixture of 4 (fluorescence due to SA), and the endocytosis marker FM 4-64 at 37 °C (image shows fluorescence in certain areas only), (c) same as (b) except with added fluorescence shown due to FM 4-64 stained endosomes, (d) same as (b) after incubation at 4 °C.
4. Figure 4.4 (a) Comparison of benzotriazole release curves from pristine halloysite, halloysite encapsulated with urea–formaldehyde encapsulation, and with copper end tube stoppers. (b) Formation of the tube end Cu-benzotriazole stoppers.
5. Figure 4.5 (a) SEM image of a dextrin cap on the end of the functionalized nanotube. (b) Resazurin assay results demonstrating the LD50 value (50% death level) of BG-loaded HNTs for Hep3b cells.
6. Figure 4.6 Schematic representation of HNTs-Cur prodrug with controlled curcumin release.
7. Figure 4.7 MTS test for the cell viability of 8505C cells cultured for 72 h in the presence of f-HNT/Sil/Que.
8. Figure 4.8 The biological mechanisms of internalization of nanotubes: (a) membrane piercing, (b) calveolae-mediated endocytosis, (c) phagocytosis, and (d) clatrin-mediated endocytosis.
9. Figure 4.9 Carbon nanotubes imaging and tracking on a plasmonic gold substrate at 37 °C during endocytosis.
10. Figure 4.10 Schematic illustration of HNT endocytosis process. (Adapted from Massaro et al. 2016 [72] and Liu et al. 2015 [90].)
11. Figure 4.11 Enhanced dark-field microscopy of HNTs taken up byA549 human cells in monolayer. Inset indicates the penetration of HNTs into cell in suspension culture. Note the perinuclear distribution of nanotubes.
12. Figure 4.12 Illustration of the HNT-g-COS synthesis and doxorubicine loading process and uptake process of nanotubes by cells and cell apoptosis mechanism.
Chapter 5: Graphene Nanotechnology
1. Figure 5.1 (a) Graphene sheet in real space, where the black (white) circles denote A(B)-sublattice sites; $c05-math-020$ is the lattice constant and $c05-math-021$ and $c05-math-022$ are the primitive vectors. (b) First BZ of graphene. $c05-math-023$ , $c05-math-024$ , $c05-math-025$ . Note that there are three $c05-math-026$ and $c05-math-027$ points, which can be connected by the reciprocal lattice vectors. (c) Energy band structure of graphene within the irreducible BZ with the DOS. (d) 3D plot of energy band structure.
2. Figure 5.2 Structure of (a) armchair nanoribbon and (b) zigzag nanoribbon. $c05-math-033$ defines the ribbon width. (c) Energy band structure $c05-math-034$ and DOS $c05-math-035$ of armchair nanoribbons with $c05-math-036$ ( $c05-math-037$ nm) and (d) zigzag nanoribbons with $c05-math-038$ ( $c05-math-039$ nm). The inset shows the charge density distribution in real space at Fermi energy.
3. Figure 5.3 (a) Schematic magnetic structure of a zigzag ribbon with $c05-math-053$ at $c05-math-054$ . (b) Energy band structure and corresponding DOS for same parameter set.
4. Figure 5.4 Hole doping effect on edge magnetism of graphene nanoribbon. Spin–spin correlation function for a zigzag graphene nanoribbon with a finite length (a) along the zigzag edge and (b) between upper and lower edges. $c05-math-064$ is the number of holes. Here, $c05-math-065$ .
5. Figure 5.5 Energy band structure and corresponding DOS for (a) zigzag graphene nanoribbon with all the edge carbon atoms replaced by boron atoms for $c05-math-066$ = 8. The solid lines and dashed lines denote the up- and down-spin states. (b) Their spin density profiles. The calculation was performed by the first-principles calculation.
6. Figure 5.6 (a) Schematic Figure of DOS for half-metallic materials. The left (right) side shows the DOS for $c05-math-067$ - ( $c05-math-068$ -) spins. The degeneracy between two spins is lifted. Since only one of the two spin states has a finite DOS near the Fermi energy, only up spin states (in this case) contributes to electronic conduction. Thus, half-metallic materials can be a source of spin-polarized current or spin-filtering materials because the other spin states (in this case, down-spin) do not allow conduction. (b) Schematic Figure of zigzag nanoribbons with the application of a transverse electric field. (c) Energy band structures and corresponding DOS for zigzag nanoribbons with $c05-math-069$ . Here the hopping between next nearest neighbor sites is included. The applied electric field is $c05-math-070$ . The solid lines and dashed lines in (c) denote down- and up-spin states. Here the calculation was performed by the mean field Hubbard model with the Coulomb interaction of $c05-math-071$ . In addition, the second nearest neighbor hopping term with the magnitude of $c05-math-072$ is included.
Chapter 6: Nanoarchitectonics of Multilayer Shells toward Biomedical Application
1. Figure 6.1 Schematic representation of the assembled hemoglobin protein microcapsules via covalent layer-by-layer assembly.
2. Figure 6.2 Schematic illustration to show the fabrication process of Hb/DHP microcapsules through Schiff's base bond.
3. Figure 6.3 Schematic representation of the assembled Hb microspheres with the surface modified by PEG.
4. Figure 6.4 Schematic illustration of microcapsules (uploading hydrophilic DOX) coated by folate-linked lipid-encapsulating photosensitizer HB.
5. Figure 6.5 Schematic illustration of the assembly of (ADA/fLuc)_n microcapsules, bioluminescent process, and the chemical reactions.
6. Figure 6.6 The illustration shows the formulation of the co-assembled bioconjugate and two approaches against tumor cell proliferation.
7. Figure 6.7 Schematic illustration of AuNR@MSN-HB@LF.
8. Figure 6.8 Schematic illustration of folate–lipid-conjugated mesoporous silica-coated graphene oxide.
9. Figure 6.9 (A) Schematic illustration of the fabrication of TRAIL/ALG-CaCO₃ nanocomposites loaded with DOX. (B) HeLa cells co-cultured with 8 × 102 to 6 × 106 mg ml⁻¹ TRAIL/ALG-CaCO₃ nanocomposites loaded with DOX for 24 h. (C) Flow cytometry diagrams of the uptake of hollow shells by HeLa cells. (a) C cells were cultured in a normal way; (b) cells cultured with CaCO₃ nanocomposites loaded with DOX; (c) cells cultured with TRAIL/ALG-CaCO₃ nanocomposites loaded with DOX.
10. Figure 6.10 Schematic illustration of the assembly of TRAIL/ALG-DOX@BSA.
Chapter 7: Layered Nanoarchitectonics with Layer-by-Layer Assembly Strategy for Biomedical Applications
1. Figure 7.1 Schematic representation of the formation of layered nanoarchitectures with layer-by-layer assembly technique.
2. Figure 7.2 (a) The schematic representation of layer-by-layer spin coating process of polyelectrolytes. (b) A side view schematic depicting the build-up of multilayer assemblies by consecutive spinning process of anionic and cationic polyelectrolytes.
3. Figure 7.3 (A) Schematic representation of the effect of swelling of the PDDA//PSS multilayer films assembled in different NaCl solutions on NIH-3T3 cell adhesions. PDDA, poly(diallyldimethylammonium chloride); PSS, poly(sodium 4-styrenesulfonate). (B) Fibroblast morphology and cell adhesions on the PEI/PSS/(PDDA/PSS)₉ multilayer films assembled in different NaCl solutions after being plated for 12 h and 36 h, respectively: (a) without extraneous NaCl; (b) 0.15 M NaCl; (c) 0.3 M NaCl; (d) 0.5 M NaCl; (e) 1.0 M NaCl, and (f) on bare glass coverslip. For NIH-3T3 cells, actin and vinculin were stained with Fluorescein isothiocyanate (FITC)-phalloidin (bright gray) and a monoclonal anti-vinculin antibody (light gray), respectively.
4. Figure 7.4 (A) AFM images showing surface morphology (a) and the phase images (b) of (PAH/GO)₁₀/PAH/PSS multilayer films. (B) (a) Force–displacement curves of (PAH/PSS)₃₃₀, [(PAH/PSS)₅/PAH/GO/(PAH/PSS)₅]₃₀, and [(PAH/GO)₁₀/PAH/PSS]₃₀ films. Values of elastic modulus (b) and hardness (c) for the LbL multilayer films: 1, (PAH/PSS)₃₃₀; 2, [(PAH/PSS)₅/PAH/GO/(PAH/PSS)₅]₃₀; 3, [(PAH/PSS)₂/PAH/GO/(PAH/PSS)₂]₆₆; 4, (PAH/PSS/PAH/GO/PAH/PSS)₁₁₀; 5, [(PAH/GO)₁₀/PAH/PSS]₃₀.
5. Figure 7.5 (A) Atomic force microscopy (AFM) image of (graphene/PDDA-PB)₁ ultrathin film assembled on silicon wafer. (B) Photographs of (graphene/PDDAPB)n films assembled on quartz slides with increasing bilayer numbers (from one bilayer to six bilayers). (C) Cyclic voltammograms of the bare glass carbon electrode (GCE) in the presence of glucose solution (5.0 mM) (a) and the (graphene/PDDA-PB/GOx/PDDA-PB)₃ film electrode in the absence (b) and presence of 2.0 mM (c), and 5.0 mM glucose solution (d) in phosphate buffer saline (PBS) (pH 7.4) containing 0.1 M KCl at 50 mV s⁻¹. (D) Current–time amperometric response of (graphene/PDDA-PB/GOx/PDDA-PB)₃ film electrode with successive addition of glucose into stirring PBS of pH 7.4, containing 0.1 M KCl. Inset (a) is the calibration curve. Inset (b) shows the steady-state current response time of the modified electrode to 0.1 mM glucose. Applied potential: 0.2 V.
6. Figure 7.6 Schematic representation of the difference of BMP-2 presentation on films and in solution to the cell. When BMP-2 is bound to the film (left part of the scheme), it is spatially confined and its diffusion is restricted. In addition, the occupancy rate of BMP-2 receptors is enhanced with a possible formation of homo- and heterodimeric receptor complexes and ligand/receptor binding is not limited by diffusion (a high number of free ligands is available in the proximity of the receptors). Furthermore, due to the close proximity of growth factor receptors and adhesion receptors, a cross talk between these two types of receptor is possible. Thus, cross talks between BMP-2 signaling and adhesion signaling, which can induce cytoskeleton remodeling, might explain the striking effects observed for cells plated on soft films with bBMP-2. Such a cooperative effect cannot be observed when BMP-2 is presented in solution (right part of the scheme), that is, BMP-2 can freely diffuse in 3D and has a low availability due to the diffusion-limited reaction between receptors and ligands. Furthermore, in this case, BMP-2 receptors are diffusing at the plasma membrane and are not in the vicinity of adhesion receptors.
Chapter 8: Emerging 2D Materials
1. Figure 8.1 Crystal and electronic structures, and basic quantum properties of graphene. (a) Left: crystal structure of graphene and right: corresponding Brillouin zone. The Dirac cones are located at the K and K′ points. (b) Energy dispersion in the honeycomb lattice showing a zoom in of the energy band close to a Dirac point.
2. Figure 8.2 (a) Shubnikov-de Haas oscillations in graphene. (b) Quantum Hall effect of graphene.
3. Figure 8.3 Structures of CTF-1 and CTF-TCPB. Light and dark gray balls represent carbon and nitrogen atoms, respectively. Densities of states (DOSs) of CTF-1 and CTF-TCPB are calculated on the first-principle basis.
4. Figure 8.4 (a) Schematic illustration of a 2D MOF based on planar nickel bis(dithiolene) complex.
Chapter 9: Self-Assembly and Directed Assembly
1. Figure 9.1 Typical intermolecular interactions and their possible assembly manner.
2. Figure 9.2 Various kinds of amphiphiles and the illustrations of the self-assembly of amphiphiles to diverse nanostructures through a bilayer or monolayer unit.
3. Figure 9.3 (a) Typical packing modes of the π-conjugated molecules. (b) Various nanostructures from the self-assembly of ZnTPyP in aqueous CTAB solution. (c) Surfactant-assisted self-assembly of ZnTPyP via an oil-in-water way from chloroform solution to aqueous CTAB solutions to provide diverse nanostructures.
4. Figure 9.4 (a) Illustration of the self-assembly of peptides to form various nanostructures.
5. Figure 9.5 Conventional and selective directed self-assembly. (a) Directed self-assembly utilizes a substrate prepattern to impart long-range order to both lamellar and cylindrical self-assembled block copolymer films. (b) In selective directed self-assembly, a blend of block copolymers (either cylindrical or lamellar) assembles on specially designed surface chemical line gratings, leading to the simultaneous formation of coexisting ordered morphologies in separate areas of the substrate.
6. Figure 9.6 (a) Molecular structure of NBCB-b-NBPLA consisting of cyanobiphenyl mesogens (blue rod) and PLA (red), the blue plane is the inter-material dividing surface (IMDS). CB6 is the free mesogen introduced into the system to accelerate the kinetics of magnetic field alignment. (b) Magnetic alignment occurs subject to the positive anisotropy and homogeneous anchoring of the mesogens leading to orientation of cylindrical domains along the field. (c) UV irradiation yielding mechanically robust films. (d) Subsequent PLA etching from the aligned material results in a large-area nonporous membrane over millimeter-scale thicknesses.
7. Figure 9.7 Schematic illustration of DNA-directed assembly of nanoparticles by hybridizations between complementary DNA strands.
8. Figure 9.8 Self-assembly of hydrogel cubes with uniform giant DNA glue modification. (a) Schematic of giant-DNA-directed hydrogel assembly. Giant DNA containing tandem repeats of complementary 48-nt sequences was uniformly amplified on the surface of red and blue hydrogel cubes. Hybridization between the complementary DNA sequences resulted in assembly of hydrogel cubes. (b) Aggregates assembled from red and blue hydrogel cubes carrying complementary giant DNA.
9. Figure 9.9 (a) Schematic representation of the experimental setup. (b) Transmission electron microscopy and (c) scanning electron microscopy images of the building block and the one-dimensional nanocube belts, respectively.
10. Figure 9.10 General schematic illustration for preparing nanotube-aligned films by LB technique: First, TMGE nanotubes prepared by gelation upon heating and cooling in toluene and encapsulated with guest molecules using instant gelation method. The formed gel was dispersed in toluene and the tubular structures remained unchanged. Then, spreading the dispersed suspension on the water subphase, using LB technique with repeated compression and expansion procedure, well-aligned nanotube films can be obtained.
Chapter 10: Functional Porous Materials
1. Figure 10.1 2015 IUPAC classification of physisorption isotherms.
2. Figure 10.2 2015 IUPAC classification of hysteresis loops.
3. Figure 10.3 Four types of functionality: (a) framework backbones, being inorganic, organic, or inorganic–organic components; (b) ionic (either cationic or anionic) species adsorbed on the pore walls via strong ionic interactions; (c) organics covalently functionalized to the pore walls; and (d) guest species encapsulated in the porous cavities such as organic molecules, enzymes, and metal clusters.
4. Figure 10.4 Synthesis of nanoporous silica with a pore diameter near the boundary between micro- and mesopores by the orthogonal multiple interactions of SDA–SDA, SDA–silica, and silica–silica.
5. Figure 10.5 Examples of molecular structures of (a) polymers with intrinsic microporosity (PIMs), (b) hypercross-linked polymers (HCPs), and (c) conjugated microporous polymers (CMPs).
6. Figure 10.6 (a) Schematic of typical synthesis of MOFs. (b) Synthesis of MOFs in the presence of multiple ligands having different functional groups.
Chapter 11: Integrated Composites and Hybrids
1. Figure 11.1 (a) Schematic for the fabrication of a glassy carbon electrode (GCE) modified by 3D-rGO/AgNP. (b, c) SEM images for 3D-rGO/AgNP.
2. Figure 11.2 (a) Schematic of the preparation of the composite chiroptical plasmonic film by mixing aqueous suspensions of CNCs and gold NRs. TEM images of (b) CNCs and (c) gold NRs. Inset in (b) shows high magnification of the CNCs.
3. Figure 11.3 SEM images of BVO nanoplates (a) and rGO–BVO (b), SEM images of as-prepared samples (c) Bi₂₄O₃₁Br₁₀, and (d) 1.0% GR-BOB.
4. Figure 11.4 (a) Schematic illustration of the formation of the Fe/Fe₃O₄/N-carbon composite. (b, c) HRTEM images of nanocomposite C-MnO₂.
5. Figure 11.5 (a) Schematic illustration for the synthesis of the HC@MoS₂ microspheres. (b, c) SEM images of annealed HC@MoS₂ microspheres. (d, e) SEM image and TEM image of CSHPS-G.
Chapter 12: Shape-Memory Materials
1. Figure 12.1 Examples of shape-changing materials with non-programmable and programmable shape shifting: pine cone, and hydrogels as non-programmable systems; shape-memory polymers and alloys as programmable systems.
2. Figure 12.2 Molecular level mechanisms of one-way and two-way SME of the cross-linked semicrystalline polymer system. The photographs show thermally induced two-way SME and one-way quadruple SME in the SMPs.
3. Figure 12.3 Classification on the basis of type of polymer network architecture. (a) Physically cross-linked and (b) covalently cross-linked SMPs with T_g or T_m as the switching temperature. SMPs with (c) (semi)IPN and (d) composite/hybrid polymer networks as multifunctional materials.
4. Figure 12.4 SMPs with different architectures. (A) SMP fibers. The SFSC is reversibly transformed into flexural or elongated states and returned to its original shape. Smart clothes woven from SFSC enable them to fit different shapes and sizes.
5. Figure 12.5 Future applications of SMPs. (A) Concept of rbSME which enables applications such as self-sufficient grippers.
Chapter 13: Optically Active Organic Field-Effect Transistors
1. Figure 13.1 Categorization of phototransistors according to the dimensions of organic semiconductor channels: (a) 3D single crystals, (b) 2D thin films, and (c) 1D nanowires. Each category has its merits and demerits.
2. Figure 13.2 (a) Reversible changes of photochromic reactions with UV–vis light irradiation: open-/closed-ring isomerization of diarylethene (DAE), ionic/nonionic states of spiropyran, and cis-/trans-conformations of azobenzene. (b) Recent studies of photochromism in organic field-effect transistors at interfaces/surfaces, in channel/dielectric layers, and as the channel layer.
3. Figure 13.3 (a) DAE molecules are doped as “guests” into (b) a P3HT “host” semiconducting layer in (c) a bottom-gate, bottom-contact OFET.
4. Figure 13.4 (a) Spiropyran (SP) molecules are doped as “guests” into a P3HT “host” semiconducting layer. (b) Schematic illustrations of a dual-gate transistor, where phase-separated layers (SP-rich bottom layer and SP-free top layer) work as optically inert and active channels, respectively.
5. Figure 13.5 (a) Device configuration and molecular structures of DAE. (b) Transfer curves of closed- and open-ring isomers. (c) Optical switching of drain current in a DAE-based transistor.
6. Figure 13.6 (a) Setup for optical patterning and electrical measurement. (b) Absorption spectra of closed- and open-ring DAE isomers.
7. Figure 13.7 (a) Writing 1D nanowire channels by UV spotlight scanning. (b) Erasing 1D nanowire channels by vis spotlight scanning. Drain currents are increased (or decreased) with the numbers of the channels.
8. Figure 13.8 Stepwise control of drain current through a 1D channel. Drain current can be tuned by adjusting the power of the scanning UV and vis spotlight.
9. Figure 13.9 Adder circuit patterning. (a) No current in initial state, (b) zigzag channel patterned by UV₁ scanning to yield drain current I₁, (c) branched channel patterned by UV₂ to yield drain current I₂, (d) vis optical valve to close the first channel, and (e) UV optical valve to open the first channel. Multiple drain current levels, I₁, I_2, and I₁ + I₂ can be controlled by the position of optical valves.
10. Figure 13.10 Logic circuit patterning. (a) Initial state, where prepatterned electrodes are connected by a network of 1D channels in an insulator (open-ring) thin film. According to the position of the optical valves, the electrical current paths can be controlled for (b) OR and (c) AND circuits. Here, input and output signals are denoted, I₁, I₂, and O, respectively.
Chapter 14: Efficient Absorption of Sunlight Using Resonant Nanoparticles for Solar Heat Applications
1. Figure 14.1 Scattering, absorption, and extinction efficiencies of a sphere in a homogeneous medium with refractive index of 1.33. Each coefficient is calculated for x = 0.3, 0.6, and 0.9, where x is the normalized parameter in Mie theory described in the main text.
2. Figure 14.2 (a) Complex permittivities of TiN, gold (Au), and carbon (C). In wavelength, all the three permittivities are plotted from 300 to 1400 nm. (b) Analytically calculated absorption efficiencies of TiN, Au, and C nanospheres of 65-nm radii (solid line plot, left axis) in water and the normalized solar irradiance (area plot, right axis).
3. Figure 14.3 (a, b) TEM images of the TiN (a) and carbon (b) nanoparticles. (c) XRD patterns of the TiN and carbon nanoparticles. (d) Absorbance of the TiN and carbon nanoparticles in water with the same concentration where the absorbance is normalized to water.
4. Figure 14.4 (a) Schematic drawing of the experiment. (b) Time-dependent water vaporization and (c) temperature change of TiN-nanoparticle-dispersed water, carbon-nanoparticle-dispersed water, and pure water. The irradiance of the artificial sunlight was constant at 80 mW cm⁻².
5. Figure 14.5 (a) Complex permittivity of Ge in a complex permittivity plane from 300 to 1200 nm. (b) Scattering efficiency (Q_sca), absorption efficiency (Q_abs), and extinction efficiency (Q_ext) of Ge nanoparticles from 40 to 80 nm in radius in water. The inserted text shows the radius in the unit of nanometers.
6. Figure 14.6 (a) Bright-field TEM image of the Ge nanoparticles. (b) XRD patterns of the Ge nanoparticles where the indexes show Ge phase. (c) Measured and analytically calculated normalized extinction spectra of Ge nanoparticles dispersed in pure water.
7. Figure 14.7 (a) Vaporized weight and (b) temperature increase of the Ge- nanoparticle-dispersed water under the illumination of simulated sunlight at 80 mW cm⁻². The concentration of Ge nanoparticles is varied from 0 (pure water) to 0.01 vol%. The solid lines in panel (a) are smoothed curves for eye-guides.
8. Figure 14.8 Applications of nanoparticle-dispersed water for (a) solar water heating and (b) solar water distillation.
Chapter 15: Nanoarchitectonics Approach for Sensing
1. Figure 15.1 A sensor based on LbL structure of mesoporous carbon materials (CMK-3) and polyelectrolyte on a QCM plate.
2. Figure 15.2 An LbL assembly of reduced graphene oxide nanosheets and ionic liquid with selective adsorption of aromatic guest molecules.
3. Figure 15.3 Sensing profiles (frequency shifts) of various gaseous guests by the QCM sensor with the LbL film of reduced graphene oxide nanosheets and ionic liquid.
4. Figure 15.4 An LbL film of mesoporous carbon capsules with polyelectrolyte on a QCM plate.
5. Figure 15.5 Gas sensing selectivity of QCM sensors with three kinds of mesoporous carbon capsules.
6. Figure 15.6 Comparisons of dye-removal capability among (a) activated carbon, (b) carbon nanocage, and (c) conventional mesoporous carbon CMK-3: the structure of the carbon nanocage is only a simplified illustration.
7. Figure 15.7 Nanostructure carbon with cage-in-fiber structural motif on a QCM sensor plate: the structure of the carbon nanocage is only a simplified illustration.
Chapter 16: Self-Healing
1. Figure 16.1 Typical self-healing pathways of self-healing materials. (a) A self-healing event achieved by the polymerization of an encapsulated healant monomer, which is limited by healant depletion. (b) A cracked self-healing material repeatedly heals above the melting temperature of the polymer. (c) A hydrogel which cross-linked by dynamic bond self-healing cracks regardless of the temperature.
2. Figure 16.2 Self-healing behavior of the self-healing hydrogel based on a four-armed PEG-phos and metal ions.
3. Figure 16.3 Biomedically applicable self-healing materials. An injectable self-healing hydrogel can be applied for (a) drug release and (b) as a bone adhesive. (c) A self-healing tissue culture scaffold enables the production of interfacial zones between ligament, cartilage, and bone.
4. Figure 16.4 Schematic illustration of the systems of (a) 3D gel printers and (b) a self-healing template for the preparation of arbitrary hydrogels.
5. Figure 16.5 Arbitrarily shaped hydrogels synthesized by the self-healing template system. Mosaic-shaped hydrogels containing a different molar mass of poly(ethylene glycol) diacrylate (PEGDA) (a) and partially present PEGDA and poly(N-isopropyl acrylamide-co-N-hydroxymethylacrylamide) acrylate (b). A cube-like hydrogel containing an ant (c) and a matryoshka-like hydrogel (d).
Chapter 17: Materials Nanoarchitectonics: Drug Delivery System
1. Figure 17.1 Temperature difference in a living body.
2. Figure 17.2 Benzoxaborole derivatives loading or bearing materials for drug delivery system. (A) Chemical structures of (a) benzoxaborole and (b) its derivatives. (B) PLLA film.
Chapter 18: Mechanobiology
1. Figure 18.1 The hierarchical feature of cellular mechanosensitivity. (a) Mechanosensitive ion channels that respond to surface tension of lipid bilayers. (b) Mechanosensitive proteins that have cryptic binding sites. (c) Dependence of stem cell commitment on cellular shape. (d) An acquisition of an invasive phenotype in tumor cells applied with compressive stress. (e) Tensegrity models of cells, which are composed of sticks and elastic strings.
2. Figure 18.2 Applications of micropatterning to address cellar tensegrity. (a) Procedure of microcontact printing. (b,c) Dependence of (b) cell proliferation and (c) stem cell differentiation on the degree of cell spreading area.
3. Figure 18.3 Applications of micropatterning to address single-cell polarization and collective characteristics. (a) Subcellular-size adhesive-island-directed cell division axis formation.
4. Figure 18.4 Applications of dynamic cell micropatterning to cellular mechanobiology. (a) The concept of dynamic substrates. (b) Cell-shape-induced cell polarization and directed cell migration. (c) Impact of geometrical constraints on single-cell migration.
5. Figure 18.5 Nanopatterning for cellular mechanobiology. (a) Focal adhesion as biochemical and mechanical hubs in cell adhesion to ECM. (b) Procedure for block copolymer nanolithography. (c) Nano-digit surfaces clarified required minimum separation of integrin heterodimers. (d) Loss of collective migration characteristics in HeLa cells migrating on (top) nanopatterned and (below) homogenous substrates.
Chapter 19: Diagnostics
1. Figure 19.1 A sandwich ELISA. (1) Plate is coated with a capture antibody; (2) sample is added, and any antigen present binds to capture antibody; (3) detecting antibody is added, and binds to antigen; (4) enzyme-linked secondary antibody is added, and binds to detecting antibody; (5) substrate is added, and is converted by enzyme to detectable form.
2. Figure 19.2 Thermo-induced immunoseparation system using a stimuli-responsive polymer.
3. Figure 19.3 Design concept for smart diagnostic system that utilizes biomolecular-polymer-nanoparticle hybrids for enhancing analyte capture rates and assay sensitivity.
4. Figure 19.4 Stimuli-responsive fluidic system for purifying and concentrating diagnostic biomarkers using temperature-responsive antibody conjugates and membranes.
Chapter 20: Immunoengineering
1. Figure 20.1 The trade-off relationship between immune activation and immunosuppression.
2. Figure 20.2 Biological reactions and expected effects of immunoevasive, immune-activating, and immunosuppressive biomaterials. iDC, immature dendritic cell; mDC, mature dendritic cell; tDC, tolerogenic dendritic cell; Th1, T helper 1 cell; Th2, T helper 2 cell; CTL, cytotoxic T lymphocyte; Mφ, macrophage; B_reg, regulatory B cell; T_reg, regulatory T cell; Tr1, type 1 regulatory T cell.
3. Figure 20.3 Relationship between protein size and nonspecific adsorption ability on various surfaces. Surfaces modified with PEG at two different molecular weights exhibited superior antifouling properties [5].
4. Figure 20.4 (a) Targeting to dendritic cells and release of protein antigen in cells. Particles cross-linked with a pH-responsive cross-linking agent selectively disintegrate and release antigens in the acidic environment of a lysosome. (b) Polypropylic acid (PPAA)is able to disrupt the endosomal membrane due to abrupt protonation at endosomal pH because it has a pK_a around pH 6.0–6.5. (c) Antitumor effect of hyaluronic acid (HA) immobilized on HVJ-E. The HA layer improves stability in bloodstream and works as a ligand for CD44, which is overexpressed on cancer cells. In addition, as this layer diffuses in endosomal pH, HVJ-E can fuse with the endosomal membrane due to revealed fusion proteins and induce strict tumor toxicity.
5. Figure 20.5 Immune response differences in physical, geometrical, and physicochemical properties of particles. (a) Size-dependent delivery efficiency of particles to target. (b) Macrophages show phagocytosis when they adhere to the tip of elliptical particles, but they exhibit adhesion/extension behavior when they adhere to flat surfaces of elliptical particles. (c) For gold nanoparticles modified with hydrophobic and anionic domains, nanoparticles with regularly arranged surface induces cell membrane permeability, whereas nanoparticles with randomly distributed surface are endocytosed by cells.
6. Figure 20.6 Major phospholipids constituting the cell membrane and collapse of asymmetrical distribution of the phospholipid bilayer due to the progression of apoptosis. Sph, sphingomyelin; PtdCho, phosphatidylcholine; PtdEA, phosphatidylethanolamine; PtdSer, phosphatidylserine; PtdIno, phosphatidylinositol.

Materials Nanoarchitectonics

Edited by Katsuhiko Ariga and Mitsuhiro Ebara

Editors

Dr. Katsuhiko Ariga

National Inst. for Materials Science

WPI-MANA

1-1 Namiki

305-0044 Tsukuba, Ibaraki

Japan

Dr. Mitsuhiro Ebara

National Inst. for Materials Science

Mechanobiology Group

1-1 Namiki

305-0044 Tsukuba, Ibaraki

Japan

Cover Image: © Ian Cuming/Alamy Stock Photo

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