Editorial

3 pages, 178 KiB

Open AccessEditorial

Editorial of Special Issue “Functional Nanomaterials Based on Self-Assembly”

by Pavel Padnya

Nanomaterials 2023, 13(23), 3062; https://doi.org/10.3390/nano13233062 - 01 Dec 2023

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In recent years, the design and creation of new functional nanosystems and nanomaterials similar in their properties to biological systems showed remarkable progress as an interdisciplinary field of research combining chemistry, biology, and physics [...] Full article

(This article belongs to the Special Issue Functional Nanomaterials Based on Self-Assembly)

Research

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20 pages, 3950 KiB

Open AccessArticle

Voltammetric Sensor for Doxorubicin Determination Based on Self-Assembled DNA-Polyphenothiazine Composite

by Anastasiya Malanina, Yurii Kuzin, Alena Khadieva, Kseniya Shibaeva, Pavel Padnya, Ivan Stoikov and Gennady Evtugyn

Nanomaterials 2023, 13(16), 2369; https://doi.org/10.3390/nano13162369 - 18 Aug 2023

Cited by 4 | Viewed by 1064

Abstract

A novel voltammetric sensor based on a self-assembled composite formed by native DNA and electropolymerized N-phenyl-3-(phenylimino)-3H-phenothiazin-7-amine has been developed and applied for sensitive determination of doxorubicin, an anthracycline drug applied for cancer therapy. For this purpose, a monomeric phenothiazine derivative has been deposited [...] Read more.

A novel voltammetric sensor based on a self-assembled composite formed by native DNA and electropolymerized N-phenyl-3-(phenylimino)-3H-phenothiazin-7-amine has been developed and applied for sensitive determination of doxorubicin, an anthracycline drug applied for cancer therapy. For this purpose, a monomeric phenothiazine derivative has been deposited on the glassy carbon electrode from the 0.4 M H₂SO₄-acetone mixture (1:1 v/v) by multiple potential cycling. The DNA aliquot was either on the electrode modified with electropolymerized film or added to the reaction medium prior to electropolymerization. The DNA entrapment and its influence on the redox behavior of the underlying layer were studied by scanning electron microscopy and electrochemical impedance spectroscopy. The DNA–doxorubicin interactions affected the charge distribution in the surface layer and, hence, altered the redox equilibrium of the polyphenothiazine coating. The voltametric signal was successfully applied for the determination of doxorubicin in the concentration range from 10 pM to 0.2 mM (limit of detection 5 pM). The DNA sensor was tested on spiked artificial plasma samples and two commercial medications (recovery of 90–95%). After further testing on real clinical samples, the electrochemical DNA sensor developed can find application in monitoring drug release and screening new antitumor drugs able to intercalate DNA. Full article

(This article belongs to the Special Issue Functional Nanomaterials Based on Self-Assembly)

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15 pages, 2916 KiB

Open AccessArticle

Synthesis of PDMS-μ-PCL Miktoarm Star Copolymers by Combinations (Є) of Styrenics-Assisted Atom Transfer Radical Coupling and Ring-Opening Polymerization and Study of the Self-Assembled Nanostructures

by Yi-Shen Huang, Dula Daksa Ejeta, Kun-Yi (Andrew) Lin, Shiao-Wei Kuo, Tongsai Jamnongkan and Chih-Feng Huang

Nanomaterials 2023, 13(16), 2355; https://doi.org/10.3390/nano13162355 - 17 Aug 2023

Cited by 2 | Viewed by 1189

Abstract

Due to their diverse and unique physical properties, miktoarm star copolymers (μ-SCPs) have garnered significant attention. In our study, we employed α-monobomoisobutyryl-terminated polydimethylsiloxane (PDMS-Br) to carry out styrenics-assisted atom transfer radical coupling (SA ATRC) in the presence of 4-vinylbenzyl alcohol (VBA) at 0 [...] Read more.

Due to their diverse and unique physical properties, miktoarm star copolymers (μ-SCPs) have garnered significant attention. In our study, we employed α-monobomoisobutyryl-terminated polydimethylsiloxane (PDMS-Br) to carry out styrenics-assisted atom transfer radical coupling (SA ATRC) in the presence of 4-vinylbenzyl alcohol (VBA) at 0 °C. By achieving high coupling efficiency (χ_c = 0.95), we obtained mid-chain functionalized PDMS-VBA_m-PDMS polymers with benzylic alcohols. Interestingly, matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF MS) analysis revealed the insertion of only two VBA coupling agents (m = 2). Subsequently, the PDMS-VBA₂-PDMS products underwent mid-chain extensions using ε-caprolactone (ε-CL) through ring-opening polymerization (ROP) with an efficient organo-catalyst at 40 °C, resulting in the synthesis of novel (PDMS)₂-μ-(PCL)₂ μ-SCPs. Eventually, novel (PDMS)₂-μ-(PCL)₂ μ-SCPs were obtained. The obtained PDMS-μ-PCL μ-SCPs were further subjected to examination of their solid-state self-assembly through small-angle X-ray scattering (SAXS) experiments. Notably, various nanostructures, including lamellae and hexagonally packed cylinders, were observed with a periodic size of approximately 15 nm. As a result, we successfully developed a simple and effective reaction combination (Є) strategy (i.e., SA ATRC-Є-ROP) for the synthesis of well-defined PDMS-μ-PCL μ-SCPs. This approach may open up new possibilities for fabricating nanostructures from siloxane-based materials. Full article

(This article belongs to the Special Issue Functional Nanomaterials Based on Self-Assembly)

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11 pages, 3707 KiB

Open AccessArticle

Heading toward Miniature Sensors: Electrical Conductance of Linearly Assembled Gold Nanorods

by Marisa Hoffmann, Christine Alexandra Schedel, Martin Mayer, Christian Rossner, Marcus Scheele and Andreas Fery

Nanomaterials 2023, 13(9), 1466; https://doi.org/10.3390/nano13091466 - 25 Apr 2023

Cited by 1 | Viewed by 1272

Abstract

Metal nanoparticles are increasingly used as key elements in the fabrication and processing of advanced electronic systems and devices. For future device integration, their charge transport properties are essential. This has been exploited, e.g., in the development of gold-nanoparticle-based conductive inks and chemiresistive [...] Read more.

Metal nanoparticles are increasingly used as key elements in the fabrication and processing of advanced electronic systems and devices. For future device integration, their charge transport properties are essential. This has been exploited, e.g., in the development of gold-nanoparticle-based conductive inks and chemiresistive sensors. Colloidal wires and metal nanoparticle lines can also be used as interconnection structures to build directional electrical circuits, e.g., for signal transduction. Our scalable bottom-up, template-assisted self-assembly creates gold-nanorod (AuNR) lines that feature comparably small widths, as well as good conductivity. However, the bottom-up approach poses the question about the consistency of charge transport properties between individual lines, as this approach leads to heterogeneities among those lines with regard to AuNR orientation, as well as line defects. Therefore, we test the conductance of the AuNR lines and identify requirements for a reliable performance. We reveal that multiple parallel AuNR lines (>11) are necessary to achieve predictable conductivity properties, defining the level of miniaturization possible in such a setup. With this system, even an active area of only 16 µm² shows a higher conductance (~10⁻⁵ S) than a monolayer of gold nanospheres with dithiolated-conjugated ligands and additionally features the advantage of anisotropic conductance. Full article

(This article belongs to the Special Issue Functional Nanomaterials Based on Self-Assembly)

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25 pages, 6076 KiB

Open AccessArticle

Role of Polyanions and Surfactant Head Group in the Formation of Polymer–Colloid Nanocontainers

by Elmira A. Vasilieva, Darya A. Kuznetsova, Farida G. Valeeva, Denis M. Kuznetsov and Lucia Ya. Zakharova

Nanomaterials 2023, 13(6), 1072; https://doi.org/10.3390/nano13061072 - 16 Mar 2023

Cited by 2 | Viewed by 1389

Abstract

Objectives. This study was aimed at the investigation of the supramolecular systems based on cationic surfactants bearing cyclic head groups (imidazolium and pyrrolidinium) and polyanions (polyacrylic acid (PAA) and human serum albumin (HSA)), and factors governing their structural behavior to create functional nanosystems [...] Read more.

Objectives. This study was aimed at the investigation of the supramolecular systems based on cationic surfactants bearing cyclic head groups (imidazolium and pyrrolidinium) and polyanions (polyacrylic acid (PAA) and human serum albumin (HSA)), and factors governing their structural behavior to create functional nanosystems with controlled properties. Research hypothesis. Mixed PE–surfactant complexes based on oppositely charged species are characterized by multifactor behavior strongly affected by the nature of both components. It was expected that the transition from a single surfactant solution to an admixture with PE might provide synergetic effects on structural characteristics and functional activity. To test this assumption, the concentration thresholds of aggregation, dimensional and charge characteristics, and solubilization capacity of amphiphiles in the presence of PEs have been determined by tensiometry, fluorescence and UV-visible spectroscopy, and dynamic and electrophoretic light scattering. Results. The formation of mixed surfactant–PAA aggregates with a hydrodynamic diameter of 100–180 nm has been shown. Polyanion additives led to a decrease in the critical micelle concentration of surfactants by two orders of magnitude (from 1 mM to 0.01 mM). A gradual increase in the zeta potential of HAS–surfactant systems from negative to positive value indicates that the electrostatic mechanism contributes to the binding of components. Additionally, 3D and conventional fluorescence spectroscopy showed that imidazolium surfactant had little effect on HSA conformation, and component binding occurs due to hydrogen bonding and Van der Waals interactions through the tryptophan amino acid residue of the protein. Surfactant–polyanion nanostructures improve the solubility of lipophilic medicines such as Warfarin, Amphotericin B, and Meloxicam. Perspectives. Surfactant–PE composition demonstrated beneficial solubilization activity and can be recommended for the construction of nanocontainers for hydrophobic drugs, with their efficacy tuned by the variation in surfactant head group and the nature of polyanions. Full article

(This article belongs to the Special Issue Functional Nanomaterials Based on Self-Assembly)

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18 pages, 6338 KiB

Open AccessArticle

From Nano-Crystals to Periodically Aggregated Assembly in Arylate Polyesters—Continuous Helicoid or Discrete Cross-Hatch Grating?

by Cheng-En Yang, Selvaraj Nagarajan, Widyantari Rahmayanti, Chean-Cheng Su and Eamor M. Woo

Nanomaterials 2023, 13(6), 1016; https://doi.org/10.3390/nano13061016 - 11 Mar 2023

Cited by 3 | Viewed by 1088

Abstract

This work used several model arylate polymers with the number of methylene segment n = 3, 9, 10, and 12, which all crystallized to display similar types of periodically banded spherulites at various T_c and kinetic factors. Universal mechanisms of nano- to [...] Read more.

This work used several model arylate polymers with the number of methylene segment n = 3, 9, 10, and 12, which all crystallized to display similar types of periodically banded spherulites at various T_c and kinetic factors. Universal mechanisms of nano- to microscale crystal-by-crystal self-assembly to final periodic aggregates showing alternate birefringence rings were probed via 3D dissection. The fractured interiors of the birefringent-banded poly(decamethylene terephthalate) (PDT) spherulites at T_c = 90 °C revealed multi-shell spheroid bands composed of perpendicularly intersecting lamellae bundles, where each shell (measuring 4 μm) was composed of the interior tangential and radial lamellae, as revealed in the SEM results, and its shell thickness was equal to the optical inter-band spacing (4 μm). The radial-oriented lamellae were at a roughly 90° angle perpendicularly intersecting with the tangential ones; therefore, the top-surface valley band region appeared to be a submerged “U-shape”, where the interior radial lamellae were located directly underneath. Furthermore, the universal self-assembly was proved by collective analyses on the three arylate polymers. Full article

(This article belongs to the Special Issue Functional Nanomaterials Based on Self-Assembly)

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19 pages, 3727 KiB

Open AccessArticle

Doxorubicin-Loaded Polyelectrolyte Multilayer Capsules Modified with Antitumor DR5-Specific TRAIL Variant for Targeted Drug Delivery to Tumor Cells

by Anastasia Gileva, Daria Trushina, Anne Yagolovich, Marine Gasparian, Leyli Kurbanova, Ivan Smirnov, Sergey Burov and Elena Markvicheva

Nanomaterials 2023, 13(5), 902; https://doi.org/10.3390/nano13050902 - 27 Feb 2023

Cited by 2 | Viewed by 1764

Abstract

Recently, biodegradable polyelectrolyte multilayer capsules (PMC) have been proposed for anticancer drug delivery. In many cases, microencapsulation allows to concentrate the substance locally and prolong its flow to the cells. To reduce systemic toxicity when delivering highly toxic drugs, such as doxorubicin (DOX), [...] Read more.

Recently, biodegradable polyelectrolyte multilayer capsules (PMC) have been proposed for anticancer drug delivery. In many cases, microencapsulation allows to concentrate the substance locally and prolong its flow to the cells. To reduce systemic toxicity when delivering highly toxic drugs, such as doxorubicin (DOX), the development of a combined delivery system is of paramount importance. Many efforts have been made to exploit the DR5-dependent apoptosis induction for cancer treatment. However, despite having a high antitumor efficacy of the targeted tumor-specific DR5-B ligand, a DR5-specific TRAIL variant, its fast elimination from a body limits its potential use in a clinic. A combination of an antitumor effect of the DR5-B protein with DOX loaded in the capsules could allow to design a novel targeted drug delivery system. The aim of the study was to fabricate PMC loaded with a subtoxic concentration of DOX and functionalized with the DR5-B ligand and to evaluate a combined antitumor effect of this targeted drug delivery system in vitro. In this study, the effects of PMC surface modification with the DR5-B ligand on cell uptake both in 2D (monolayer culture) and 3D (tumor spheroids) were studied by confocal microscopy, flow cytometry and fluorimetry. Cytotoxicity of the capsules was evaluated using an MTT test. The capsules loaded with DOX and modified with DR5-B demonstrated synergistically enhanced cytotoxicity in both in vitro models. Thus, the use of the DR5-B-modified capsules loaded with DOX at a subtoxic concentration could provide both targeted drug delivery and a synergistic antitumor effect. Full article

(This article belongs to the Special Issue Functional Nanomaterials Based on Self-Assembly)

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12 pages, 2297 KiB

Open AccessArticle

Light-Induced Clusterization of Gold Nanoparticles: A New Photo-Triggered Antibacterial against E. coli Proliferation

by Angela Candreva, Renata De Rose, Ida Daniela Perrotta, Alexa Guglielmelli and Massimo La Deda

Nanomaterials 2023, 13(4), 746; https://doi.org/10.3390/nano13040746 - 16 Feb 2023

Cited by 11 | Viewed by 1710

Abstract

Metallic nanoparticles show plasmon resonance phenomena when irradiated with electromagnetic radiation of a suitable wavelength, whose value depends on their composition, size, and shape. The damping of the surface electron oscillation causes a release of heat, which causes a large increase in local [...] Read more.

Metallic nanoparticles show plasmon resonance phenomena when irradiated with electromagnetic radiation of a suitable wavelength, whose value depends on their composition, size, and shape. The damping of the surface electron oscillation causes a release of heat, which causes a large increase in local temperature. Furthermore, this increase is enhanced when nanoparticle aggregation phenomena occur. Local temperature increase is extensively exploited in photothermal therapy, where light is used to induce cellular damage. To activate the plasmon in the visible range, we synthesized 50 nm diameter spherical gold nanoparticles (AuNP) coated with polyethylene glycol and administered them to an E. coli culture. The experiments were carried out, at different gold nanoparticle concentrations, in the dark and under irradiation. In both cases, the nanoparticles penetrated the bacterial wall, but a different toxic effect was observed; while in the dark we observed an inhibition of bacterial growth of 46%, at the same concentration, under irradiation, we observed a bactericidal effect (99% growth inhibition). Photothermal measurements and SEM observations allowed us to conclude that the extraordinary effect is due to the formation, at low concentrations, of a light-induced cluster of gold nanoparticles, which does not form in the absence of bacteria, leading us to the conclusion that the bacterium wall catalyzes the formation of these clusters which are ultimately responsible for the significant increase in the measured temperature and cause of the bactericidal effect. This photothermal effect is achieved by low-power irradiation and only in the presence of the pathogen: in its absence, the lack of gold nanoparticles clustering does not lead to any phototoxic effect. Therefore, it may represent a proof of concept of an innovative nanoscale pathogen responsive system against bacterial infections. Full article

(This article belongs to the Special Issue Functional Nanomaterials Based on Self-Assembly)

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10 pages, 2594 KiB

Open AccessArticle

Solid Lipid Nanoparticles Based on Monosubstituted Pillar[5]arenes: Chemoselective Synthesis of Macrocycles and Their Supramolecular Self-Assembly

by Darya Filimonova, Anastasia Nazarova, Luidmila Yakimova and Ivan Stoikov

Nanomaterials 2022, 12(23), 4266; https://doi.org/10.3390/nano12234266 - 30 Nov 2022

Cited by 1 | Viewed by 1063

Abstract

Novel monosubstituted pillar[5]arenes with one or two terminal carboxyl groups were synthesized by the reaction of succinic anhydride with pillar[5]arene derivative containing a diethylenetriamine function. The ability for non-covalent self-assembly in chloroform, dimethyl sulfoxide, as well as in tetrahydrofuran-water system was studied. The [...] Read more.

Novel monosubstituted pillar[5]arenes with one or two terminal carboxyl groups were synthesized by the reaction of succinic anhydride with pillar[5]arene derivative containing a diethylenetriamine function. The ability for non-covalent self-assembly in chloroform, dimethyl sulfoxide, as well as in tetrahydrofuran-water system was studied. The ability of the synthesized macrocycles to form different types of associates depending on the substituent nature was established. The formation of stable particles with average diameter of 192 nm in chloroform and of 439 nm in DMSO was shown for pillar[5]arene containing two carboxyl fragments. Solid lipid nanoparticles (SLN) based on monosubstituted pillar[5]arenes were synthesized by nanoprecipitation in THF-water system. Minor changes in the structure of the macrocycle substituent can dramatically influence the stability and shape of SLN (spherical and rod-like structures) accordingly to DLS and TEM. The presence of two carboxyl groups in the macrocycle substituent leads to the formation of stable spherical SLN with an average hydrodynamic diameter of 364–454 nm. Rod-like structures are formed by pillar[5]arene containing one carboxyl fragment, which diameter is about of 50–80 nm and length of 700–1000 nm. The synthesized stable SLN open up great prospects for their use as drug storage systems. Full article

(This article belongs to the Special Issue Functional Nanomaterials Based on Self-Assembly)

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14 pages, 7325 KiB

Open AccessArticle

New Approach to Non-Invasive Tumor Model Monitoring via Self-Assemble Iron Containing Protein Nanocompartments

by Anna N. Gabashvili, Maria V. Efremova, Stepan S. Vodopyanov, Nelly S. Chmelyuk, Vera V. Oda, Viktoria A. Sarkisova, Maria K. Leonova, Alevtina S. Semkina, Anna V. Ivanova and Maxim A. Abakumov

Nanomaterials 2022, 12(10), 1657; https://doi.org/10.3390/nano12101657 - 12 May 2022

Cited by 4 | Viewed by 2104

Abstract

According to the World Health Organization, breast cancer is the most common oncological disease worldwide. There are multiple animal models for different types of breast carcinoma, allowing the research of tumor growth, metastasis, and angiogenesis. When studying these processes, it is crucial to [...] Read more.

According to the World Health Organization, breast cancer is the most common oncological disease worldwide. There are multiple animal models for different types of breast carcinoma, allowing the research of tumor growth, metastasis, and angiogenesis. When studying these processes, it is crucial to visualize cancer cells for a prolonged time via a non-invasive method, for example, magnetic resonance imaging (MRI). In this study, we establish a new genetically encoded material based on Quasibacillus thermotolerans (Q.thermotolerans, Qt) encapsulin, stably expressed in mouse 4T1 breast carcinoma cells. The label consists of a protein shell containing an enzyme called ferroxidase. When adding Fe²⁺, a ferroxidase oxidizes Fe²⁺ to Fe³⁺, followed by iron oxide nanoparticles formation. Additionally, genes encoding mZip14 metal transporter, enhancing the iron transport, were inserted into the cells via lentiviral transduction. The expression of transgenic sequences does not affect cell viability, and the presence of magnetic nanoparticles formed inside encapsulins results in an increase in T2 relaxivity. Full article

(This article belongs to the Special Issue Functional Nanomaterials Based on Self-Assembly)

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20 pages, 2978 KiB

Open AccessArticle

Self-Healing Thiolated Pillar[5]arene Films Containing Moxifloxacin Suppress the Development of Bacterial Biofilms

by Dmitriy N. Shurpik, Yulia I. Aleksandrova, Olga A. Mostovaya, Viktoriya A. Nazmutdinova, Regina E. Tazieva, Fadis F. Murzakhanov, Marat R. Gafurov, Pavel V. Zelenikhin, Evgenia V. Subakaeva, Evgenia A. Sokolova, Alexander V. Gerasimov, Vadim V. Gorodov, Daut R. Islamov, Peter J. Cragg and Ivan I. Stoikov

Nanomaterials 2022, 12(9), 1604; https://doi.org/10.3390/nano12091604 - 09 May 2022

Cited by 11 | Viewed by 2041

Abstract

Polymer self-healing films containing fragments of pillar[5]arene were obtained for the first time using thiol/disulfide redox cross-linking. These films were characterized by thermogravimetric analysis and differential scanning calorimetry, FTIR spectroscopy, and electron microscopy. The films demonstrated the ability to self-heal through the action [...] Read more.

Polymer self-healing films containing fragments of pillar[5]arene were obtained for the first time using thiol/disulfide redox cross-linking. These films were characterized by thermogravimetric analysis and differential scanning calorimetry, FTIR spectroscopy, and electron microscopy. The films demonstrated the ability to self-heal through the action of atmospheric oxygen. Using UV–vis, 2D 1H-1H NOESY, and DOSY NMR spectroscopy, the pillar[5]arene was shown to form complexes with the antimicrobial drug moxifloxacin in a 2:1 composition (logK11 = 2.14 and logK12 = 6.20). Films containing moxifloxacin effectively reduced Staphylococcus aureus and Klebsiella pneumoniae biofilms formation on adhesive surfaces. Full article

(This article belongs to the Special Issue Functional Nanomaterials Based on Self-Assembly)

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Review

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22 pages, 8774 KiB

Open AccessReview

Supramolecular Nanostructures Based on Perylene Diimide Bioconjugates: From Self-Assembly to Applications

by Nadjib Kihal, Ali Nazemi and Steve Bourgault

Nanomaterials 2022, 12(7), 1223; https://doi.org/10.3390/nano12071223 - 05 Apr 2022

Cited by 16 | Viewed by 4073

Abstract

Self-assembling π-conjugated systems constitute efficient building blocks for the construction of supramolecular structures with tailored functional properties. In this context, perylene diimide (PDI) has attracted attention owing to its chemical robustness, thermal and photo-stability, and outstanding optical and electronic properties. Recently, the conjugation [...] Read more.

Self-assembling π-conjugated systems constitute efficient building blocks for the construction of supramolecular structures with tailored functional properties. In this context, perylene diimide (PDI) has attracted attention owing to its chemical robustness, thermal and photo-stability, and outstanding optical and electronic properties. Recently, the conjugation of PDI derivatives to biological molecules, including oligonucleotides and peptides, has opened new avenues for the design of nanoassemblies with unique structures and functionalities. In the present review, we offer a comprehensive summary of supramolecular bio-assemblies based on PDI. After briefly presenting the physicochemical, structural, and optical properties of PDI derivatives, we discuss the synthesis, self-assembly, and applications of PDI bioconjugates. Full article

(This article belongs to the Special Issue Functional Nanomaterials Based on Self-Assembly)

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