Polymeric Micro/Nanocarriers and Motors for Cargo Transport and Phototriggered Delivery
Abstract
:1. Introduction
2. Organic and Polymeric Micro/Nanocarriers
2.1. Liposomes
2.2. Polymeric Micro/Nanomicelles
2.3. Micro/Nanopolymersomes
2.4. Polymeric Micro/Nanospheres
3. Photosensitive Polymeric Micro/Nanocarriers
3.1. Photoisomerizable and Photocleavable Molecues
3.2. Photoactive Polymers: Synthesis and Assembly
3.3. Photostimulation Mechanisms for Cargo Delivery
3.4. Characterization of Photosensitive Micro/Nanocarriers
3.4.1. Cargo Loading Capacity and Encapsulation Efficiency
3.4.2. Cargo Photorelease
4. Photosensitive Polymeric Nanomicelles
5. Photo-Stimulated Organic and Polymeric Nanocarriers for Cargo Delivery
5.1. Photosensitive Liposomes and Polymeric Nanoconjugates
5.2. Photosensitive Nanopolymersomes
6. Functionalization of Phototriggered Nanocarriers for Targeting Cells
7. Polymeric Micro/Nanomotors for Cargo Transport
7.1. Definition and Classification
7.1.1. Propelled by Light
7.1.2. Propelled by Magnetic Fields and Catalytic Reactions
7.1.3. Propelled by Enzymes
7.1.4. Propelled by Electrophoresis, Diffusiophoresis, and the Marangoni Effect
8. Some Applications of Light-Stimulated Polymeric Micro/Nanomotors
8.1. Propulsion, Cargo Transport, and Drug Delivery
8.2. Environmental Control and Remediation
8.3. Biosensing and Cancer Therapeutics
9. Current Challenges, Opportunities, and Concluding Remarks
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Characterization Parameter | Method | Comment | Ref. |
---|---|---|---|
Morphological and physicochemical | FT-IR | The absorption spectroscopy technique works via application of a polychromatic infrared beam over a compound in liquid, solid, or gaseous state. | [159] |
The infrared spectrum is obtained via the Fourier transform mathematical process, in a wavenumber range between 4000 cm−1 and 660 cm−1. | [160] | ||
Chemical functional groups—such as carboxylic, hydroxy, and amine groups, among many others—absorb and transmit infrared light at different wavenumbers, characterizing the PMNs’ organic composition. | [161,162] | ||
NMR | Structural characterization technology in which an oscillating magnetic field disturbs a nucleus molecule, producing a particular electromagnetic signal. | [163] | |
The frequency of this signal depends on the chemical structure and nonzero nuclear spin of the involved isotope. | [164] | ||
1H NMR is a spectrometric method that uses the magnetic moment and angular momentum of the hydrogen-1 nucleus to obtain its frequency characteristics, which depend on the atom–proton interaction, such as C–H and O–H, determining the molecular structure of the PMNs. | [165,166] | ||
TEM | The micro/nanoscale image capture method detects the transmitted electrons after irradiation with an electron beam over a target sample. | [167] | |
The staining technique from TEM permits differentiation between nanopolymersomes, nanomicelles, and nanospheres, because the hydrophobic core and interface of the micelles and polymersomes are stained for differentiation via dark electron absorption (Figure 2B,C, respectively). | [168,169,170] | ||
SEM | Electron-beam-based technique that scans the sample’s surface via electron–atom interaction, characterizing its topography and composition. | [171] | |
The spheres with a high density of hydrophobic and hydrophilic segments can be visualized via SEM (Figure 4D). | |||
Morphological and physicochemical | TEM and SEM | Characterizes morphology, size, and elemental composition of the PMNs. | [172] |
DLS | Uses an optical mode to quantify the scattered light beam for the particles dispersed in the medium, characterizing the size distribution of PMNs, concerning the sample’s intensity extent, volume, or number. | [173,174] | |
SLS | Estimates the molecular weight of NPs in the solution. | [175] | |
ELS | Describes the static electric field intensity on the double-layer limit from a particle/molecule dispersed in a fluid. | [176] | |
The superficial charge known as ζ-potential determines the PMNs’ dispersity and the electron density characteristics of the available groups on the nanoparticles’ surface. | [177] | ||
Fluorescence spectroscopy | Quantifies a compound’s light emission after electron excitation via light beam irradiation. | [178] | |
Absorbance spectroscopy | Spectrophotometric method characterized by wavelength-dependent absorption of a compound after light irradiation. | [179] | |
Absorbance spectroscopy describes the photoisomerization and photocleavage mechanism by absorbing the PAMs’ characteristic wavelength peaks. | [154,156] | ||
Fluorescence and absorbance spectroscopy | Allows tracking and quantification of the presence of fluorescence and absorbance of loaded and photoreleased cargo in the PMNs, such as Nile red, doxorubicin, Dil, etc. | [147,157,180] | |
Cargo LC, EE, and photorelease | Gravimetry, titrimetry, and potentiometry | Employed to quantify the concentration of a compound photoreleased from PMNs. | [181] |
Gravimetry | Quantitative measurement of the solid analyte weight to concentration determination. | [182] | |
Titrimetry | The quantitative chemical analysis uses neutralization reactions to measure a solution’s concentration via volumetric or potentiometric techniques. | [183] | |
Interaction between the solutions involved in the reactions and an indicator that generates a color change characterizes the volumetric techniques to calculate the volumes’ concentration. | [184] | ||
Potentiometry | Employs the turning points of the pH–volume curve between the target and the known solution in order to determine the hydrogen cation concentration and, indirectly, the concentrations of some compounds. | [185] | |
Cargo LC, EE, and photorelease | Chromatography | Methods characterized by a physical separation, employing the mobile and stationary phases of the molecules involved in the process in gas and liquid states to quantify their concentrationa. | [186,187] |
High-performance liquid chromatography (HPLC) quantifies cargo concentration by separating mobile and stationary liquid phases in order to establish the LC and EE. | [188] | ||
Spectrophotometry and fluorescence spectroscopy | Commonly used to quantify the cargo concentration via UV–Vis absorption and fluorescence intensity techniques, using the cargo absorbance or fluorescence curves regarding concentration and weight—either directly in the loaded cargo or indirectly in the supernatant (free cargo)—and then determining the LC and EE. | [189] | |
Spectrophotometry is the most commonly used method to quantify the delivered cargo, because of its straightforward use, taking advantage of the cargo absorption and fluorescence properties, as characterized by UV–Vis absorption and fluorescence techniques. | [190,191] | ||
Movement | Tracking analysis | Motion videos are taken by high-resolution cameras adapted to optical and fluorescence microscopy. They are then analyzed using tracking software or programs such as Image J to quantify the velocity and distance traveled by the particles. | [192,193,194] |
Nanoparticle trace analysis (NTA) | Nanoparticles’ motion is analyzed in solution using NanoSight for particles between 10 and 1000 nm in size. Each particle is analyzed individually using NTA, via direct observation and measurement of diffusion events. | [195,196] |
Type | PAMs | Features | Application | Ref. |
---|---|---|---|---|
Polymeric nanomicelles | Azobenzene | 30s/UV light/365 nm/photoisomerization | Concept of cargo photodelivery | [211] |
5 min/UV light/365 nm/photoisomerization | Hydrophobic model drug (Nile red) photorelease | [180] | ||
UV light/365 nm/photoisomerization | Hydrophobic model drug (Curcumin) photorelease | [212] | ||
14 s/UV light/365 nm/photoisomerization | Concept of specific cargo photorelease into cells | [146] | ||
O-nitrobenzyl | 30 min/UV light/365 nm/photocleavage | Drug/gene/protein photodelivery | [213] | |
Polymeric nanomicelles | O-nitrobenzyl | 60 min/NIR irradiation/765nm/photocleavage | Drug model photorelease in deep tissues | [149] |
Liposomes | Azobenzene | UV light/365 nm/photoisomerization | Doxorubicin delivery | [226] |
O-nitrobenzyl | NIR irradiation photocleavage | Concept of cargo photodelivery | [227] | |
NIR irradiation/740 nm/pcCPP-linked | siRNA photodelivery into specific cells | [249] | ||
Phospholipid-PEG nanoparticles | Fluorophore model | NIR irradiation ≥ 1000 nm/anti-EGFR antibody-linked | NIR fluorescence in vivo imaging of MDA-MB-468 cells | [246] |
Nanopolymersomes | Azobenzene | UV light/360 nm/photoisomerization | Photorelease of hydrophilic and hydrophobic molecules | [147] |
O-nitrobenzyl | UV light/365 nm/photocleavage | Photorelease of hydrophobic doxorubicin -release as potential use in cancer therapy | [140] | |
UV light/360 nm/photocleavage | Doxorubicin photodelivery into HeLa cells | [222] | ||
Nanospheres based on UCNPs | O-nitrobenzyl | 60 min/NIR irradiation/980 nm/photocleavage | Model drug delivery into cells for enhancing neocartilage formation in vivo | [220] |
NIR irradiation/980 nm/adamantane-dimer-targeting peptide-linked | Drug photodelivery into cancer cells | [247] | ||
Polymeric nanospheres | Verteporfin photosensitizer | NIR irradiation/690 nm/hTfr peptide-linked | Phototriggered treatment of breast cancer | [248] |
DTRCD | NIR irradiation/660 nm/ROS photogeneration | Specific drug delivery into cell nuclei and enhanced cancer therapy | [250] |
Motor | Propulsion Mechanism | Features | Application | Ref. |
---|---|---|---|---|
Janus capsule based on silica particles and gold | Thermophoresis triggered by light | NIR irradiation/808 nm/1–20 μm diameter/42 μm s−1 speed | Dynamic strategy for cancer therapy | [301] |
Polymeric tubular rocket | NIR irradiation/780 nm/10 μm length and 5 μm width/160 μm s−1 speed | Fuel-free and externally controlled propulsion for biomedical applications | [302] | |
Polymeric Janus microcapsules | Magneto-catalytic reaction triggered by the Pt–H2O2 system | ~150 μm diameter/200–2400 μm s−1 speed | Potential usefulness of soft micromotors for targeted delivery of cargo | [310] |
Janus polymeric sphere | Catalytic reaction from the Mg–HCl system | ~20 μm diameter/~120 μm s−1 speed | Antibiotic drug delivery for bacterial burden reduction in the murine stomach | [311] |
Tubular polymersome | Catalytic reaction from the catalase–H2O2 system | 300 nm size | Hydrophobic and hydrophilic model drug delivery | [313] |
Protein- and phospholipid-based Janus droplets | Hydrolysis reaction from the urease–urea and lipase system | 22–80 µm size/2–41 µm s−1 speed | New Janus particle formation via fusion mechanism | [318] |
Self-fueled lipase-active oil droplets | Buoyancy mechanism motion | 10 of 60 µm of oil droplets/membrane thickness of 7.46 nm | New lipase droplet for protocell buoyancy-induced motion | [319] |
Polymeric Janus stomatocyte | Catalytic reaction from the Pt–H2O2 system | 345 nm diameter/~35 μm s−1 speed | Cargo delivery in a cellular environment | [312] |
Nanorods | Electrophoresis triggered by UV or visible light | 3 μm length and 150 nm radius/21 ± 4 μm s−1 speed | Propulsion concept | [323] |
Janus Ag-Cl | Diffusiophoresis | 2.5 μm diameter | 3D cargo transport and sensing applications | [324] |
Tubular | Marangoni effect by the surfactant at tubular surface | Enzyme delivery | Pollutant degradation | [326] |
Polymeric sphere | Photoisomerization triggered by light | UV and visible irradiation/16 nm diameter/15 μm s−1 speed | Light-stimulated propulsion | [341] |
Janus polymersome | Thermophoresis stimulated by NIR irradiation | 100 nm diameter/6.2 μm s−1 speed | Doxorubicin delivery into HeLa cancer cells | [345] |
Janus polymersome | Catalytic reaction caused by Pt–H2O2 | 749.2–2634.2 nm diameter/2–90 μm s−1 speed | Drug photodelivery | [350] |
Magnetic chitosan microswimmers | Magnetic motion at 10 mT and 4.5 Hz | 3.34 ± 0.71 μm s−1 | Doxorubicin photocleavage release | [351] |
Janus BiOI microspheres | Electrophoresis stimulated by visible light | 2~4 μm diameter/1.62 μm s−1 speed | Fuel-free motion strategy | [346] |
Organic polymeric systems | Photocatalysis of semiconductor polymers under visible light | 6.5 μm diameter/1.82 μm s−1 speed | Colorimetric-based acidity sensors | [347] |
Polymeric Janus microparticle | Magneto-catalytic motion from the Pt–H2O2 system | Fluorescent phenylboronic acid and graphene-modified GQDs | Detection of lipopolysaccharides for biomedical and biological applications | [248] |
Polymeric Janus nanoparticle | Catalytic reaction from the Pt–H2O2 system | NIR thermal polymer | Photothermal therapy | [349] |
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Mena-Giraldo, P.; Orozco, J. Polymeric Micro/Nanocarriers and Motors for Cargo Transport and Phototriggered Delivery. Polymers 2021, 13, 3920. https://doi.org/10.3390/polym13223920
Mena-Giraldo P, Orozco J. Polymeric Micro/Nanocarriers and Motors for Cargo Transport and Phototriggered Delivery. Polymers. 2021; 13(22):3920. https://doi.org/10.3390/polym13223920
Chicago/Turabian StyleMena-Giraldo, Pedro, and Jahir Orozco. 2021. "Polymeric Micro/Nanocarriers and Motors for Cargo Transport and Phototriggered Delivery" Polymers 13, no. 22: 3920. https://doi.org/10.3390/polym13223920