Materials Nanoarchitectonics E-Book
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- Herausgeber: Wiley-VCH Verlag GmbH & Co. KGaA
- Kategorie: Wissenschaft und neue Technologien
- Sprache: Englisch
A unique overview of the manufacture of and applications for materials nanoarchitectonics, placing otherwise hard-to-find information in context.
Edited by highly respected researchers from the most renowned materials science institute in Japan, the first part of this volume focuses on the fabrication and characterization of zero to three-dimensional nanomaterials, while the second part presents already existing as well as emerging applications in physics, chemistry, biology, and biomedicine.
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Seitenzahl: 609
Veröffentlichungsjahr: 2018
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Table of Contents
Cover
Title Page
Copyright
Chapter 1: Change Thinking toward Nanoarchitectonics
1.1 From Nanotechnology to Nanoarchitectonics
1.2 Way of Nanoarchitectonics
1.3 Materials Nanoarchitectonics
References
Part I: Zero- and One-Dimensional Nanoarchitectonics
Chapter 2: Architectonics in Nanoparticles
2.1 Introduction
2.2 Soft Nanoparticles
2.3 Hierarchical Architecturing of Solid Nanoparticles
2.4 Janus (Asymmetric) Nanoparticles
2.5 Functional Architectures on the Surface of Nanoparticles
2.6 Summary
References
Chapter 3: Aspects of One-Dimensional Nanostructures: Synthesis, Characterization, and Applications
3.1 Introduction
3.2 Synthesis of NCs
3.3 Growth Mechanisms of 1D Nanocrystals
3.4 Post-Synthetic Modification
3.5 Essential Characterization Techniques
3.6 Promising Applications of 1D NCs
3.7 Summary and Conclusions
References
Chapter 4: Tubular Nanocontainers for Drug Delivery
4.1 Introduction
4.2 Carbon Nanotubes for Drug Delivery
4.3 Halloysite-Nanotube-Based Carriers for Drug Delivery
4.4 Tubular Nanosized Drug Carriers: Uptake Mechanisms
4.5 Conclusions
References
Part II: Two-Dimensional Nanoarchitectonics
Chapter 5: Graphene Nanotechnology
5.1 Introduction
5.2 Electronic States of Graphene
5.3 Graphene Nanoribbons and Edge States
5.4 Spintronic Properties of Graphene
5.5 Summary
References
Chapter 6: Nanoarchitectonics of Multilayer Shells toward Biomedical Application
6.1 Introduction
6.2 Hollow-Structured Multilayers
6.3 Multilayer Shells on Template
6.4 Summary and Outlook
Acknowledgments
References
Chapter 7: Layered Nanoarchitectonics with Layer-by-Layer Assembly Strategy for Biomedical Applications
7.1 Layer-by-Layer Assembly Technique
7.2 LbL-Assembled Layer Architectures with Tunable Properties
7.3 The Application of the LbL-Assembled Layer Architectures in Biomedicine
7.4 Summary and Outlook
Acknowledgment
References
Chapter 8: Emerging 2D Materials
8.1 Introduction
8.2 Revisiting Uniqueness of Graphene as the Archetype of 2D Materials Systems
8.3 Emerging 2D Materials
8.4 Remarks
Acknowledgment
References
Part III: Three-Dimensional and Hierarchic Nanoarchitectonics
Chapter 9: Self-Assembly and Directed Assembly
9.1 Introduction
9.2 Amphiphile Self-Assembly
9.3 π-Conjugated Molecule Self-Assembly
9.4 Peptide Self-Assembly
9.5 Self-Assembly of Block Polymers
9.6 DNA-Directed Self-Assembly
9.7 Directed Self-Assembly of Nanoparticles
9.8 LB-Technique-Directed Alignment of Nanostructures
9.9 Conclusions
References
Chapter 10: Functional Porous Materials
10.1 Introduction
10.2 Classification of Porous Materials
10.3 Functional Frameworks: from Inorganic, through Organic, to Inorganic–Organic
10.4 Summary and Outlook
References
Chapter 11: Integrated Composites and Hybrids
11.1 3D Hybrid Nanoarchitectures Assembled from 0D and 2D Nanomaterials
11.2 3D Hybrid Nanoarchitectures Assembled from 1D and 2D Nanomaterials
11.3 3D Hybrid Nanoarchitectures Assembled from 2D and 2D Nanomaterials
11.4 Other Approaches to 3D Hybrid Nanoarchitectures
11.5 Conclusion
References
Chapter 12: Shape-Memory Materials
12.1 Introduction
12.2 Fundamentals of Shape-Memory Effect in Polymers
12.3 Categorization of Shape-Memory Polymers on the Basis of Nanoarchitectonics
12.4 Shape-Memory Polymers with Different Architectures
12.5 New Directions in the Field of Shape-Memory Polymers
12.6 Conclusions
References
Part IV: Materials Nanoarchitectonics for Application 1: Physical and Chemical
Chapter 13: Optically Active Organic Field-Effect Transistors
13.1 Introduction
13.2 Phototransistors
13.3 Photochromism in OFETs
13.4 Summary and Perspectives
References
Chapter 14: Efficient Absorption of Sunlight Using Resonant Nanoparticles for Solar Heat Applications
14.1 Introduction
14.2 Electromagnetic Analysis for Finding the Resonance Conditions of Nanoparticles
14.3 Plasmon Resonance Nanoparticles for Sunlight Absorption
14.4 Mie Resonance Nanoparticles for Sunlight Absorption
14.5 Applications of Resonant Nanoparticles
14.6 Summary
Acknowledgments
References
Chapter 15: Nanoarchitectonics Approach for Sensing
15.1 Introduction
15.2 Layered Mesoporous Carbon Sensor
15.3 Layered Graphene Sensor
15.4 Hierarchic Carbon Capsule Sensor
15.5 Cage-in-Fiber Sensor
15.6 Summary
References
Chapter 16: Self-Healing
16.1 Introduction
16.2 History of Self-Healing Materials
16.3 Dynamic Cross-links to Construct a Self-Healing Hydrogel Network
16.4 Further Applications of Self-Healing Materials
16.5 Conclusion
References
Part V: Materials Nanoarchitectonics for Application 2: Biological and Biomedical
Chapter 17: Materials Nanoarchitectonics: Drug Delivery System
17.1 Introduction
17.2 Conclusion and Future Trends
References
Chapter 18: Mechanobiology
18.1 Introduction
18.2 Micropatterning Cellular Shape and Cluster Geometry
18.3 Dynamic Micropatterning Single Cells and Cell Collectives
18.4 Nanopatterning Cell–Extracellular Matrix Interactions
18.5 Concluding Remarks
References
Chapter 19: Diagnostics
19.1 Introduction
19.2 Immunoassays
19.3 Nucleic Acid Tests
19.4 Stimuli-Responsive Biomarker Separations
19.5 Stimuli-Responsive Diagnostics in the Developing World
19.6 Conclusions
References
Chapter 20: Immunoengineering
20.1 Introduction
20.2 Immunoevasive Biomaterials
20.3 Immune-Activating Biomaterials
20.4 Immunosuppressive Biomaterials
20.5 Conclusions
References
Index
End User License Agreement
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Guide
Cover
Table of Contents
Begin Reading
List of Illustrations
Chapter 1: Change Thinking toward Nanoarchitectonics
Figure 1.1 Fabrication characteristics at different size scales and nanoarchitectonics concept.
Chapter 2: Architectonics in Nanoparticles
Figure 2.1 The scheme for nanoparticles with various architectures.
Figure 2.2 Logic gate nanoparticles that show a dual response to reactive oxygen species (ROS) and low pH.
Figure 2.3 Programmable self-assembly of nucleic acid nanoparticles for targeted
in vivo
siRNA delivery.
Figure 2.4 Template-directed formation of multicompartment mesoporous silica nanoparticles with branched shapes.
Figure 2.5 Polymeric micelles for the synthesis of mesoporous platinum nanospheres.
Figure 2.6 Self-templated formation of flake-shelled silica capsule with morphology flexibility to stimuli.
Figure 2.7 Scalable and rapid fabrication of functionalized particles by spray-assisted layer-by-layer PRINT process.
Figure 2.8 Engineering homogeneous doping in upconversion nanoparticles by successive layer-by-layer process.
Figure 2.9 The formation of soft, nanoscale Janus particles with tunable Janus balance by triblock terpolymers.
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
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.
Figure 3.2 (a) TEM image of CdSe NRs with size of 4 nm × 20 nm, synthesized using organometallic method.
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.
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 SnTe
4
4−
in DMSO. (c) Comparison of
I–V
characteristics for the film of dodecanethiol-capped Au NCs and Sn
2
S
6
4−
capped Au NCs.
Figure 3.5 Systematic transformation of CdS NRs into Cu
2
S and then PbS NRs through cation exchange reaction. (a) TEM images of as-synthesized CdS, (b) intermediate Cu
2
S, and (c) the final PbS NRs. The arrows indicate the order of cation exchange products. (d) Absorption spectra for CdS, Cu
2
S, and PbS NRs. (e) XRD patterns for the corresponding NRs. The lines under the spectra are the JCPDS patterns for each material.
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).
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.
Figure 3.8 (A) Current–voltage (
J–V
) characteristics of a CIS NWs photovoltaic device. Inset: TEM images of CIS NWs.
Figure 3.9 (a) TEM image of CdSe NWs. Inset: AFM image of a network of NWs formed on a SiO
2
/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.
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 N
2
.
Chapter 4: Tubular Nanocontainers for Drug Delivery
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.
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 Fe
3
O
4
nanoparticles on the surface via chemical co-precipitation method; (c) External loading of gemcitabine by physical adsorption.
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.
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.
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.
Figure 4.6 Schematic representation of HNTs-Cur prodrug with controlled curcumin release.
Figure 4.7 MTS test for the cell viability of 8505C cells cultured for 72 h in the presence of f-HNT/Sil/Que.
Figure 4.8 The biological mechanisms of internalization of nanotubes: (a) membrane piercing, (b) calveolae-mediated endocytosis, (c) phagocytosis, and (d) clatrin-mediated endocytosis.
Figure 4.9 Carbon nanotubes imaging and tracking on a plasmonic gold substrate at 37 °C during endocytosis.
Figure 4.10 Schematic illustration of HNT endocytosis process. (Adapted from Massaro
et al
. 2016 [72] and Liu
et al
. 2015 [90].)
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.
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
Figure 5.1 (a) Graphene sheet in real space, where the black (white) circles denote A(B)-sublattice sites; is the lattice constant and and are the primitive vectors. (b) First BZ of graphene. , , . Note that there are three and 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.
Figure 5.2 Structure of (a) armchair nanoribbon and (b) zigzag nanoribbon. defines the ribbon width. (c) Energy band structure and DOS of armchair nanoribbons with ( nm) and (d) zigzag nanoribbons with ( nm). The inset shows the charge density distribution in real space at Fermi energy.
Figure 5.3 (a) Schematic magnetic structure of a zigzag ribbon with at . (b) Energy band structure and corresponding DOS for same parameter set.
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. is the number of holes. Here, .
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 = 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.
Figure 5.6 (a) Schematic Figure of DOS for half-metallic materials. The left (right) side shows the DOS for - (-) 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 . Here the hopping between next nearest neighbor sites is included. The applied electric field is . 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 . In addition, the second nearest neighbor hopping term with the magnitude of is included.
Chapter 6: Nanoarchitectonics of Multilayer Shells toward Biomedical Application
Figure 6.1 Schematic representation of the assembled hemoglobin protein microcapsules via covalent layer-by-layer assembly.
Figure 6.2 Schematic illustration to show the fabrication process of Hb/DHP microcapsules through Schiff's base bond.
Figure 6.3 Schematic representation of the assembled Hb microspheres with the surface modified by PEG.
Figure 6.4 Schematic illustration of microcapsules (uploading hydrophilic DOX) coated by folate-linked lipid-encapsulating photosensitizer HB.
Figure 6.5 Schematic illustration of the assembly of (ADA/fLuc)
n
microcapsules, bioluminescent process, and the chemical reactions.
Figure 6.6 The illustration shows the formulation of the co-assembled bioconjugate and two approaches against tumor cell proliferation.
Figure 6.7 Schematic illustration of AuNR@MSN-HB@LF.
Figure 6.8 Schematic illustration of folate–lipid-conjugated mesoporous silica-coated graphene oxide.
Figure 6.9 (A) Schematic illustration of the fabrication of TRAIL/ALG-CaCO
3
nanocomposites loaded with DOX. (B) HeLa cells co-cultured with 8 × 102 to 6 × 106 mg ml
−1
TRAIL/ALG-CaCO
3
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 CaCO
3
nanocomposites loaded with DOX; (c) cells cultured with TRAIL/ALG-CaCO
3
nanocomposites loaded with DOX.
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
Figure 7.1 Schematic representation of the formation of layered nanoarchitectures with layer-by-layer assembly technique.
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.
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.
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
.
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.
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
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.
Figure 8.2 (a) Shubnikov-de Haas oscillations in graphene. (b) Quantum Hall effect of graphene.
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.
Figure 8.4 (a) Schematic illustration of a 2D MOF based on planar nickel bis(dithiolene) complex.
Chapter 9: Self-Assembly and Directed Assembly
Figure 9.1 Typical intermolecular interactions and their possible assembly manner.
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.
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.
Figure 9.4 (a) Illustration of the self-assembly of peptides to form various nanostructures.
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.
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.
Figure 9.7 Schematic illustration of DNA-directed assembly of nanoparticles by hybridizations between complementary DNA strands.
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.
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.
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
Figure 10.1 2015 IUPAC classification of physisorption isotherms.
Figure 10.2 2015 IUPAC classification of hysteresis loops.
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.
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.
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).
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
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.
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.
Figure 11.3 SEM images of BVO nanoplates (a) and rGO–BVO (b), SEM images of as-prepared samples (c) Bi
24
O
31
Br
10
, and (d) 1.0% GR-BOB.
Figure 11.4 (a) Schematic illustration of the formation of the Fe/Fe
3
O
4
/N-carbon composite. (b, c) HRTEM images of nanocomposite C-MnO
2
.
Figure 11.5 (a) Schematic illustration for the synthesis of the HC@MoS
2
microspheres. (b, c) SEM images of annealed HC@MoS
2
microspheres. (d, e) SEM image and TEM image of CSHPS-G.
Chapter 12: Shape-Memory Materials
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.
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.
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.
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.
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
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.
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.
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.
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.
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.
Figure 13.6 (a) Setup for optical patterning and electrical measurement. (b) Absorption spectra of closed- and open-ring DAE isomers.
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.
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.
Figure 13.9 Adder circuit patterning. (a) No current in initial state, (b) zigzag channel patterned by UV
1
scanning to yield drain current
I
1
, (c) branched channel patterned by UV
2
to yield drain current
I
2
, (d) vis optical valve to close the first channel, and (e) UV optical valve to open the first channel. Multiple drain current levels,
I
1
,
I
2,
and
I
1
+
I
2
can be controlled by the position of optical valves.
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,
I
1
,
I
2
, and
O
, respectively.
Chapter 14: Efficient Absorption of Sunlight Using Resonant Nanoparticles for Solar Heat Applications
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.
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).
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.
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
.
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.
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.
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.
Figure 14.8 Applications of nanoparticle-dispersed water for (a) solar water heating and (b) solar water distillation.
Chapter 15: Nanoarchitectonics Approach for Sensing
Figure 15.1 A sensor based on LbL structure of mesoporous carbon materials (CMK-3) and polyelectrolyte on a QCM plate.
Figure 15.2 An LbL assembly of reduced graphene oxide nanosheets and ionic liquid with selective adsorption of aromatic guest molecules.
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.
Figure 15.4 An LbL film of mesoporous carbon capsules with polyelectrolyte on a QCM plate.
Figure 15.5 Gas sensing selectivity of QCM sensors with three kinds of mesoporous carbon capsules.
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.
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
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.
Figure 16.2 Self-healing behavior of the self-healing hydrogel based on a four-armed PEG-phos and metal ions.
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.
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.
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
Figure 17.1 Temperature difference in a living body.
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
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.
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.
Figure 18.3 Applications of micropatterning to address single-cell polarization and collective characteristics. (a) Subcellular-size adhesive-island-directed cell division axis formation.
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.
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
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.
Figure 19.2 Thermo-induced immunoseparation system using a stimuli-responsive polymer.
Figure 19.3 Design concept for smart diagnostic system that utilizes biomolecular-polymer-nanoparticle hybrids for enhancing analyte capture rates and assay sensitivity.
Figure 19.4 Stimuli-responsive fluidic system for purifying and concentrating diagnostic biomarkers using temperature-responsive antibody conjugates and membranes.
Chapter 20: Immunoengineering
Figure 20.1 The trade-off relationship between immune activation and immunosuppression.
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.
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].
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 p
K
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.
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.
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.
List of Tables
Chapter 19: Diagnostics
Table 19.1 The ideal rapid test: ASSURED criteria
Chapter 20: Immunoengineering
Table 20.1 Ionic biocompatible polymers
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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Chapter 1Change Thinking toward Nanoarchitectonics
Katsuhiko Ariga and Masakazu Aono
World Premier International (WPI) Research Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, 305-0044, Japan
1.1 From Nanotechnology to Nanoarchitectonics
Innovations in science and technology are initiated by necessity. We say that necessity is the mother of invention. In addition, finding and preparing new materials have seriously affected the progress and development of science and technology. What we want and what we have are driving forces of innovations in science and technology. We wanted to see the stars in the universe. This desire created a telescope, but it could be invented only with transparent glass materials and their fabrication. Further technological progresses led to incredible innovations. Development of microscale fabrication techniques of similar materials such as silicon opened up a huge technological success in integrated electric circuits. The latter developments induced progress that led to the current information technology (IT) revolution. Therefore, the mother of science and technology would be a social reform with advanced computers. We now expect that further advancements in the nanoscale region would create large-scale progress in science and technology, the so-called nanotechnology. With nanotechnology, various dreams are expected to come true.
Initiation of the nanotechnology concept is generally said to have come from the words “There's plenty of room at the bottom,” which anticipated the current trends in the science of nanosized objects. Much later, advancements in analytical tools such as various microscopies, including high-resolution electron microscopes and scanning probe microscopies, enabled us to directly observe nanoscale objects and structures. Although various scientific efforts in the area of nanoscale objects resulted in huge scientific progress, technological improvements even in the microscale created immense progress in micro-device technologies. Micro-devices with high density of functional structures have been mostly fabricated by the so-called top-down fabrication techniques. However, we have already realized the fatal problems in this success story. According to Moore's law, fabrication and miniaturization of device structures at the current rate in silicon-based technology will encounter the physical limits of device dimensions in the very near future. The alternate approach, the bottom-up approach, to architect functional systems from nanoscale units is now awaited.
1.2 Way of Nanoarchitectonics
A paradigm shift from technology to architectonics in nanoscale science and technology is necessary. This will result in the historical turning point from nanotechnology to nanoarchitectonics.
In order to clarify the fundamental meaning of nanoarchitectonics, we briefly compare material creation and fabrication in all the scales (Figure 1.1). In the macroscopic scale (visible-scale worlds), our craft hobbies, carpentry work, and building construction can be done according to their design drawing and blueprints. We can create and fabricate materials and structures with 100% probability if we just obey the appropriate design. We can easily expect fabrication results from design. This principle can be applicable to fabrications in microscopic scales also. Fabrication in the microscopic invisible scale, the so-called microfabrication, can be done with advanced technologies such as photolithography. These fabrication processes within invisible scales can be also done exactly based on predetermined structural design. Fabrication of microscale objects exactly reflects their design drawings in microfabrication techniques. We can basically assign and expect structures and properties of the fabricated objects from their predesigned drawings in microscopic scale.
Figure 1.1 Fabrication characteristics at different size scales and nanoarchitectonics concept.
When the scale of systems is reduced to submicron scale and nanoscale, unexpected disturbances and fluctuations have significant influences and fabrication of materials and systems become partially uncontrollable. Therefore, these fabrication processes are not always done decisively according to their predesigned drawings. Materials in nanoscale regions cannot fundamentally exclude the influence of thermal/statistical fluctuations and mutual interactions. These uncontrollable factors are inevitably included between component atoms, molecules, and materials.
Therefore, fabrication of materials and functionalization of systems have to be done with a new paradigm, nanoarchitectonics [1–7]. This novel terminology, nanoarchitectonics (nano + architecto + nics), in this meaning, was first used by Masakazu Aono in the year 2000 at the 1st International Symposium on Nanoarchitectonics Using Suprainteractions in Tsukuba, Japan. In scientific literature, Hecht first used this terminology in the title in 2003.
1.3 Materials Nanoarchitectonics
Materials production and fabrication with nanoarchitectonics can be generally done by concerted harmonization of various interactions. These fabrication effects have to be accomplished together with various techniques to control materials organization, which stimulates spontaneous processes such as self-assembly and self-organization. Methods and techniques in nanoarchitectonics include regulation and manipulation of structures as in atomic/molecular manipulation, chemical (organic reaction) and physicochemical modification, and organization upon application of external physical stimuli. Harmonization and combination of these effects and techniques correspond to architecting systems and materials rather than to a simple assembly of techniques (technology).
Nanoarchitectonics approaches are roughly summarized as follows.
1.
Reliable nanomaterials or nanosystems are created by organizing nanoscale structures (nanoparts), even with some unavoidable unreliability.
2.
The main players are not the individual nanoparts but their interactions, which cause a new functionality to emerge.
3.
Unexpected emergent functionalities can result from assembling or organizing a huge number of nanoparts.
4.
A new theoretical field, including conventional first-principles computations, is combined with novel bold approximations.
In these days, nanoarchitectonics for materials, or materials nanoarchitectonics, has spread to many fields including molecular machines and nanocars [8], amphiphilic assembly [9, 10], control of molecular inclusion [11, 12], supramolecular recognition [13–15], thin-film fabrications and functions [16–22], graphene fabrication [23], nanocarbon assembly [24–26], synthesis of mesoporous materials [27, 28], fabrication of hybrid materials and integrated systems [29–33], catalysis [34, 35], environmental remediation [36], photocatalytic removal of pollutants [37, 38], optoelectronic applications [39, 40], capacitors [41], batteries [42, 43], sensors [44–46], heterojunctions for photonic functions [47], assembly of biomolecules such as biomimetic light harvesting [48], DNA and enzymes [49–51], nucleic acid delivery [52], drug delivery [53], cell adhesion control [54], nanomedicine [55], biological applications of inorganic materials [56], bioimaging [57, 58], and dynamic functions from molecules to structures of macroscopic size [59, 60].
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Part IZero- and One-Dimensional Nanoarchitectonics
Chapter 2Architectonics in Nanoparticles
Qingmin Ji1,2, Xinbang Liu2 and Ke Yin3
1Nanjing University of Science and Technology, Herbert Gleiter Institute of Nanoscience, 200 Xiaolingwei, Nanjing, 210094, China
2Nanjing University of Science and Technology, School of Materials Science and Engineering, 200 Xiaolingwei, Nanjing, 210094, China
3Electric Power Simulation and Control Engineering Center, Nanjing Institute of Technology, No. 1 Hongjing Avenue, Jiangning Science Park, Nanjing, 211167, China
2.1 Introduction
Within the field of nanotechnology, zero-dimensional nanoparticles are one of the most prominent and promising candidates for technological applications [1]. Taking a close look at their impact in the research areas, we can get impressive lists of studies or applications of nanoparticles in fields including biomedical, energy, electronics, sensors, catalysis, filtrates, and so on. With the intensive developments in nanoscience and nanotechnology, the creation of novel nanostructures requires not only high regularity but also high complexity, which poses great challenges to the fabrication of nanoparticles. Architectonics of nanoparticles, which means the manipulation at micro and nano dimensions, will impart multifunctions of nanostructures and explore a range of new properties or applications (Figure 2.1) [2]. The concept of architectonics of nanoparticles is involved in the harmonization of various techniques and phenomena including chemical fabrications and structural control induced by physical stimuli and self-assembly/organization [3]. In this section, we focus on the recent research efforts in the creation of architectured nanoparticles through synthesis strategies.
Figure 2.1 The scheme for nanoparticles with various architectures.
According to the material nature of nanoparticles, they can be “soft” nanoparticles, which are based on polymers or molecular assemblies, or “hard” nanoparticles, which are made up of metals, inorganic materials, or their hybrids. Herein, we briefly introduce the design and fabrication of novel nanostructured nanoparticles, highlighting the principles and mechanisms of architectonics. We also summarize their related superior properties from the architectured nanoparticles.
2.2 Soft Nanoparticles
The design of “soft” nanoparticles can be traced back to the emergence of nanotechnology in the past decades. It became an important part of research in nanoscience and has met intensive investigations due to their high application potentials in electronic, photonic, or biotechnology [4]. Especially for the applications in biomedicine, soft nanoparticles with well-defined architectures and functionalities may satisfy the need to combine bulk loading, target delivery, and stimuli-responsive release. The improvement in properties and the discovery of new functionalities by structural architecturing are key goals for the design of soft nanoparticles.
2.2.1 Smart Polymer Nanoparticles
Polymer nanoparticles have constituted by far the most studied “soft” particles in the literature. In general, they can be distinguished into two major families according to their applications. One is related to drug delivery or biomedical applications, and the other is for electronic or optoelectronic properties.
2.2.1.1 Multi-Responsive Polymer Nanoparticles for Biological Therapy
A number of synthetic or natural polymers have been studied and used for biomedical applications [5]. However, only limited molecules could be used as constituents of drug delivery vesicles, due to the drastic concerns of toxicity and biocompatibility. The backbone chemistry of polymer nanoparticles may affect their stability, biodegradability, biocompatibility, biodistribution, and cellular fate. Therefore, the precise control over the nanostructures from both the chemical and physical traits is critically important in the design of polymer nanoparticles for biomedical delivery applications. Attractive “smart” properties of polymer nanoparticles can be modulated to be responsive to pH, enzymes, temperature, and even external stimuli like near-infrared (IR) or UV–vis irradiation, magnetic fields, or ultrasound vibrations [6].
The pH- and temperature-responsive nanoparticles are among the most studied dual-sensitive nanosystems. On the basis of the pH- or temperature-sensitive components, the further incorporation with functional additives in the structures may accomplish more visualized responses according to the external stimuli. Lin and coworkers constructed pH- and temperature-sensitive hydrogel nanoparticles with dual photoluminescence (PL) for bioprobes [7]. The hydrogel nanoparticles consisted of the thermo- and pH-responsive copolymers of poly(N-isopropylacrylamide) (PNIPAM) and poly(acrylic acid) (PAA). A red-emission rare-earth complex and a blue-emission quaternary ammonium tetraphenylethylene derivative (d-TPE) with similar excitation wavelengths are inserted into the hydrogel nanoparticles. The PL intensities of the nanoparticles show a linear temperature response in the range from 10 to 80 °C (red emission) and a linear pH response between pH 6.5 and 7.6 (blue emission). These dual-emission nanoparticles provide highly sensitive detection in the case of cancer cells. They can act as a quite promising sensing platform, which has potential applications in biology and chemistry, including bio- or chemosensors, biological imaging, cancer diagnosis, and externally activated release of anticancer drugs.
Smartness of the novel responsive systems relies on the structural design according to the requirements of the specific delivery. For example, oxidative stress and a reduced pH are important stimuli targets for intracellular delivery and for delivery to diseased tissue. Ideal materials were thus required to be able to deliver bioactive agents selectively under those conditions. Almutairi and coworkers designed a pH- and oxidation-responsive nanoparticle based on polythioether ketal, which can undergo programmed degradation in response to reactive oxygen species (ROS) and acidic pH (Figure 2.2) [8]. This dual-sensitive nanoparticles functioned akin to an “AND” logic gate in circuits. The polymeric backbone transforms from hydrophobic to hydrophilic following exposure to ROS, which then allows rapid acid-catalyzed degradation of ketal groups under mildly acidic environments. These responses finally accelerate the release of ovalbumin inside the nanoparticles. Cellular uptake studies proved that these dual-sensitive nanoparticles delivered and released fluorescence-labeled ovalbumin into macrophage cells much more efficiently than poly(lactic-co-glycolic acid) (PLGA) nanoparticles.
Figure 2.2 Logic gate nanoparticles that show a dual response to reactive oxygen species (ROS) and low pH.
(Adapted from Mahmoud et al. 2011 [8].)
