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Structural Nanomedicine

From EverybodyWiki Bios & Wiki

Structural nanomedicine is an emerging field that emphasizes the rational design of architecturally precise nanoscale therapeutics to maximize both their potency and safety.[1][2][3][4][5]

The principles of structural nanomedicine are used by researchers to construct nanoscale therapies with control over both composition and structure, including active drug and carrier identity, active component number and spatial arrangement, and linker chemistry. These parameters are systematically tuned to maximize performance. In structural nanomedicine, it is essential to understand structure-function relationships because even small changes in structure can influence how well a nanomedicine functions – including how it enters cells, circulates in the body, activates the immune system, or engages with its biological target.

Background

Previously, small-molecule drugs dominated the pharmaceutical landscape. Within this class of medicines, it became increasingly evident that subtle structural modifications, such as the substitution of single atoms in a molecule or the use of its enantiomer (the mirror image of a molecule), can profoundly influence biological activity. For instance, the (S)-enantiomer of ibuprofen, a commonly used small molecule drug, is significantly less effective than its (R)-enantiomer.[6]

In recent years, significant advances have been made in the development of biologics – drugs made of biological and medicinal components like nucleic acids, peptides, and proteins. Biologics have now surpassed small molecules as the dominant class of pharmaceuticals on the market. They are bigger in size and allow for customization that is not possible with small molecules. For example, antibody-drug conjugates (ADCs) can be constructed using site-specific conjugation strategies to achieve uniform drug-to-antibody ratios (DARs).[7] Similarly, bispecific antibodies (e.g., Blinatumomab)[8] have been used to demonstrate that molecular orientation, linker design, and physicochemical properties can profoundly influence therapeutic efficacy. Now, more and more nanomedicines are being used in pharma. Many of these are in the form of co-assembled superstructures; however, the field is moving toward the development of molecularly defined versions of structural nanomedicines because there are vast opportunities to tailor such drugs to maximize both efficacy and safety (Figure 1).

Figure 1. In structural nanomedicine, drugs are developed using tailorable, modular nanoscale platforms. A spectrum of complex materials can be developed from the unstructured medicinal components to create co-assembled superstructures and ultimately structured and molecularly well-defined nanomedicines. Figure adapted from[1][2]

Structural nanomedicine principles and design considerations

Structural nanomedicines encompass a range of architectures that vary in their structural precision; however, all classes of them are more structured than the unstructured medicinal components of which they are comprised (Figure 1). Many conventional nanomedicines can be classified as co-assembled superstructures; they are inherently heterogeneous, and individual nanomedicines in each batch are not structurally identical. For example, the lipid nanoparticles used in mRNA based COVID-19 vaccines vary in size, shape, and/or composition batch-to-batch, and are typically characterized based on average structural properties.[9][10][11][12]

These clinically efficacious nanoparticles are typically generated through self-assembly, so the process is scalable, but the inability to precisely define and synthesize optimal structural configurations with atomic and molecular precision (i.e., attain a globally optimized vs. a locally optimized drug) contributes to variability in pharmacokinetics and ultimately therapeutic outcomes. To address this challenge, researchers are working to rationally design well-defined, molecularly precise nanoarchitectures via systematic investigations that allow the potency and safety to be optimized across a vast design space.[citation needed]

Progress in this field is fueled by collaboration across chemistry, physics, materials science, engineering, biology, and medicine, with researchers working together to translate structural nanomedicines into clinically effective therapies. Structural nanomedicine marks a major paradigm shift in drug development; the field is moving beyond co-assembled nanoscale systems to structurally precise, mulitfunctional nanotherapeutics designed to track and treat a wide array of diseases, spanning many forms of cancers and infectious diseases (Figure 1).

Key classes of structural nanomedicines

Structural nanomedicine represents a paradigm shift in drug development: structure as well as composition are critical in engineering optimized nanomedicines designed to treat the individual patient. Notable examples of structural nanomedicines include COVID-19 mRNA vaccines, spherical nucleic acids (SNAs), megamolecules, and chemoflares.[1][2][13]

Lipid Nanoparticles (LNPs)

Lipid nanoparticles are nanoscale systems composed of ionizable lipids, cholesterol, phospholipids, and polyethylene glycol (PEG)-lipid conjugates. These co-assembled superstructures are widely used for the delivery of nucleic acids and other therapeutic agents (e.g., siRNA, CRISPR-based gene editing machinery, proteins) for the treatment of a variety of diseases and disorders.[10] LNPs gained global attention through their use in mRNA COVID-19 vaccine formulations.[14]

Researchers have focused on optimizing LNP structural properties to improve delivery efficiency and target specificity. For instance, modifications to surface charge, fluidity, and ligand presentation have been shown to influence endosomal escape, nucleic acid stability, and payload release kinetics.[citation needed]

Spherical Nucleic Acids (SNAs)

Spherical nucleic acids (SNAs) are a class of nanostructures composed of a nanoparticle core surrounded by a radially oriented, densely packed nucleic acid shell. Invented by Chad Mirkin in 1996,[15] SNAs exhibit unique properties arising from their three-dimensional architecture including enhanced cellular uptake, resistance to nuclease degradation, and low toxicity (compared to the same sequences of linear, free nucleic acids).

Clinically, SNAs have shown promise in treating glioblastoma, psoriasis, and Merkel cell carcinoma as well as other diseases and disorders, with several drug candidates in development (NCT03086278, NCT03684785, NCT03020017). In some cases, SNA-based therapies have resulted in complete remission in multiple checkpoint inhibitor–refractory cancer patients.[16] SNAs have been extensively studied in the context of gene regulation, CRISPR-based gene editing,[17][18][19] immunotherapy, and vaccine development.[20][21] These findings underscore the power of SNAs, and structural nanomedicines more broadly, in transforming therapeutic outcomes (Figure 2).

Figure 2: Harnessing the modular nature of the spherical nucleic acid (SNA) platform for structural nanomedicine. Fundamental studies involving linker chemistry (top) and antigen placement (top and bottom) have identified that specific structural arrangements can change SNA drugs from being mildly effective to curative. Figure adapted from[2][4][5]

DNA dendrons

DNA dendrons are well-defined, highly branched oligonucleotide structures. These programmable, multivalent architectures enable precise control over DNA strand number, spatial orientation, and density.[22] [23] DNA dendrons composed of therapeutic oligonucleotides have enhanced hybridization efficiencies and improved targeting and binding affinities. Their multivalency enhances cellular uptake—especially by antigen-presenting cells (APCs, a class of cells of the immune system)—and facilitates the co-delivery of peptides, proteins, or adjuvants.[22][23] Their modularity makes them useful for a variety of biomedical applications spanning drug delivery to biosensing.[24]

Chemoflares and RNA-responsive constructs

Chemoflares are a class of cell-responsive nanotherapeutics that are based on the SNA architecture,[13][25][26] and they integrate both sensing and therapeutic functions (theranostics). Developed by Natalie Artzi and others (Figure 3 top), chemoflares can be designed to release therapeutic payloads in diseased cells in response to molecular cues that are absent in healthy cells. This action is accompanied by signal (fluorescence) turn-on. For example, chemoflares have been engineered to deliver the chemotherapeutic agent 5-fluorouracil (5-FU) upon binding with mRNA targets (like MRP1) intercellularly that are known to be overexpressed in certain types of cancer cells.[27][28]

Broadly, cell-responsive nucleic acid nanomedicines can be constructed to have nucleic acid valencies and orientations that allow for therapeutic release in response to other disease-specific cues, such as pH, enzyme activity, and analyte expression (Figure 3 bottom).

Figure 3: Schematics of chemoflares composed of gold nanoparticles conjugated to hairpin DNA embedded with 5-FU chemotherapeutics. The hairpin changes conformation and releases the drug in response to hybridization with a target multidrug resistance-associated protein-1 (MRP-1) mRNA that is present in certain cancer cells. Using these structures, resistance has been reversed, and tumor elimination has been enhanced in a triple-negative breast cancer mouse model (top). Representative FIT-Flare and ProSNA nanostructures that enter cells in high quantities and respond to biological cues to function either as detection, therapeutic, or theranostic materials (bottom). Figure adapted from[1]

MegaMolecules

MegaMolecules are structurally well-defined protein assemblies invented by Milan Mrksich. These structures are prepared using site-specific covalent linkages between enzyme-tagged fusion proteins and synthetic linkers bearing irreversible inhibitors.[29] For example, megamolecules can be bispecific antibody mimics, capable of engaging both tumor antigens and T cell receptors, to bolster immune responses[30] (Figure 4).

Figure 4. (A) MegaMolecules are assembled by reacting fusion proteins containing enzyme domains with linkers presenting covalent inhibitors for the enzymes. Figure adapted from[30]

By varying the spatial arrangement and number of antigen-binding fragments (Fabs), researchers have demonstrated their ability to improve tumor cell killing. In parallel, other groups have used modular DNA scaffolds to organize different antibodies in exact stoichiometries and oligomeric sequences.[31] These approaches enable the construction of antibody mimics with precise control over domain orientation and valency. Collectively, these platforms offer a versatile strategy for the development of next-generation protein therapeutics with customizable structures and properties.

DNA origami

Predictable DNA base-pairing interactions can be used to organize long oligonucleotide strands[32][33] into DNA origami scaffolds with precise dimensions and topologies. Drugs, enzymes, antigens, and/or imaging agents can be organized upon such materials (Figure 5 top).

Figure 5: (top) Schematic of scaffolded DNA origami nanoparticles (NP) designed to self-assemble HIV immunogen eOD-GT8 in a controlled manner. (bottom) The data indicate that DNA-NP modified with eOD-GT8 activate IgM-BCR in a concentration-dependent manner. ​

The field of DNA nanotechnology was pioneered by Nadrian Seeman using tile-based approaches, and was developed further by Paul Rothemund, who introduced systems that take advantage of scaffolding and staple strands for the synthesis of very complex 2D and 3D DNA origami assemblies.[34]

These DNA-based constructs have been employed as agents for controlled drug release via molecular logic gates and stimuli-responsive features.[35] The platform has been shown to improve pharmacological targeting, minimizing off-target effects, especially in cancer and gene therapy applications (Figure 5). Recent studies have also emphasized the value of DNA origami-based immunotherapies and vaccine carriers.[36][37]

References

  1. ↑ 1.0 1.1 1.2 1.3 Mirkin CA, Mrksich M, Artzi N (July 2025). "The emerging era of structural nanomedicine". Nature Reviews Bioengineering. 3 (7): 526–528. doi:10.1038/s44222-025-00306-5. PMC 12263095 Check |pmc= value (help). PMID 40671716 Check |pmid= value (help). Unknown parameter |pmc-embargo-date= ignored (help)
  2. ↑ 2.0 2.1 2.2 2.3 Mirkin CA, Langer R, Mrksich M, Margolin AA, Petrosko SH, Artzi N (May 13, 2025). "Blueprints for Better Drugs: The Structural Revolution in Nanomedicine". ACS Nano. 19 (20): 18889–18901. Bibcode:2025ACSNa..1918889M. doi:10.1021/acsnano.5c06380. PMC 12168243 Check |pmc= value (help). PMID 40359339 Check |pmid= value (help). Unknown parameter |pmc-embargo-date= ignored (help)
  3. ↑ Kudruk S, Forsyth CM, Dion MZ, Hedlund Orbeck JK, Luo J, Klein RS, et al. (August 2, 2024). "Multimodal neuro-nanotechnology: Challenging the existing paradigm in glioblastoma therapy". Proceedings of the National Academy of Sciences. 121 (32): e2413733121. doi:10.1073/pnas.2413733121. PMC 11317605 Check |pmc= value (help). PMID 39093950 Check |pmid= value (help).
  4. ↑ 4.0 4.1 Teplensky MH, Evangelopoulos M, Dittmar JW, Forsyth CM, Sinegra AJ, Wang S, et al. (January 30, 2023). "Multi-antigen spherical nucleic acid cancer vaccines". Nature Biomedical Engineering. 7 (7): 911–927. doi:10.1038/s41551-022-01000-2. PMC 10424220 Check |pmc= value (help). PMID 36717738 Check |pmid= value (help).
  5. ↑ 5.0 5.1 Wang S, Qin L, Skakuj K, Huang Z, Chen PC, et al. (May 8, 2019). "Rational vaccinology with spherical nucleic acids". Proceedings of the National Academy of Sciences. 116 (21): 10473–10481. Bibcode:2019PNAS..11610473W. doi:10.1073/pnas.1902805116. PMC 6535021 Check |pmc= value (help). PMID 31068463.
  6. ↑ Evans, AM (February 22, 2014). "omparative pharmacology of S(+)-ibuprofen and (RS)-ibuprofen". Clin Rheumatol. 20 (Suppl 1): 9–14. doi:10.1007/BF03342662. PMID 11771573.
  7. ↑ Beck A, Goetsch L, Dumontet C, et al. (May 2017). "Strategies and challenges for the next generation of antibody-drug conjugates". Nat Rev Drug Discov. 16 (5): 315–337. doi:10.1038/nrd.2016.268. PMID 28303026.
  8. ↑ Bargou R, Leo E, Zugmaier G, Klinger M, Goebeler M, Knop S, et al. (2008). "Tumor Regression in Cancer Patients by Very Low Doses of a T Cell–Engaging Antibody". Science. 321 (5891): 974–977. Bibcode:2008Sci...321..974B. doi:10.1126/science.1158545. PMID 18703743.
  9. ↑ Kulkarni JA, Witzigmann D, Thomson SB, Chen S, Leavitt BR, Cullis PR, et al. (2021). "The current landscape of nucleic acid therapeutics". Nature Nanotechnology. 16 (6): 630–643. Bibcode:2021NatNa..16..630K. doi:10.1038/s41565-021-00898-0. PMID 34059811 Check |pmid= value (help).
  10. ↑ 10.0 10.1 Hou X, Zaks T, Langer R, Dong Y (2021). "Lipid nanoparticles for mRNA delivery". Nature Reviews Materials. 6 (12): 1078–1094. Bibcode:2021NatRM...6.1078H. doi:10.1038/s41578-021-00358-0. PMC 8353930 Check |pmc= value (help). PMID 34394960 Check |pmid= value (help).
  11. ↑ Akinc A, Zumbuehl A, Goldberg M, Leshchiner ES, Busini V, Hossain N, et al. (2008). "A combinatorial library of lipid-like materials for delivery of RNAi therapeutics". Nat Biotechnol. 26 (5): 561–569. doi:10.1038/nbt1402. PMC 3014085. PMID 18438401.
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  14. ↑ Patel R, Kaki M, Potluri VS, Kahar P, Khanna D (2022). "A comprehensive review of SARS-CoV-2 vaccines: Pfizer, Moderna & Johnson & Johnson". Human Vaccines & Immunotherapeutics. 18 (1): 1–12. doi:10.1080/21645515.2021.2002083. PMC 8862159 Check |pmc= value (help). PMID 35130825 Check |pmid= value (help). Unknown parameter |article-number= ignored (help)
  15. ↑ Mirkin CA, Letsinger RL, Mucic RC, Storhoff JJ (1996). "A DNA-based method for rationally assembling nanoparticles into macroscopic materials". Nature. 382 (6592): 607–609. Bibcode:1996Natur.382..607M. doi:10.1038/382607a0. PMID 8757129.
  16. ↑ ODay S, Perez C, Wise-Draper T, Hanna G, Bhatia S, Kelly C, et al. (2020). "Safety and Preliminary Efficacy of Intratumoral Cavrotolimod (AST-008), a Spherical Nucleic Acid TLR9 Agonist, in Combination with Pembrolizumab in Patients with Advanced Solid Tumors". Journal for Immunotherapy of Cancer. 8 (Suppl. 3): A257–A258. doi:10.1136/jitc-2020-SITC2020.0423.
  17. ↑ Rosi NL, Giljohann DA, Thaxton CS, Lytton-Jean AK, Han MS, Mirkin CA (2006). "Oligonucleotide-modified gold nanoparticles for intracellular gene regulation". Science. 312 (5776): 1027–30. Bibcode:2006Sci...312.1027R. doi:10.1126/science.1125559. PMID 16709779.
  18. ↑ Kumthekar P, Ko CH, Paunesku T, Dixit K, Sonabend AM, Bloch O, et al. (2021). "A first-in-human phase 0 clinical study of RNA interference-based spherical nucleic acids in patients with recurrent glioblastoma". Sci Transl Med. 13 (584). doi:10.1126/scitranslmed.abb3945. PMC 8272521 Check |pmc= value (help). PMID 33692132 Check |pmid= value (help). Unknown parameter |article-number= ignored (help)
  19. ↑ Huang C, Han Z, Evangelopoulos M, Mirkin CA (2022). "CRISPR Spherical Nucleic Acids". Journal of the American Chemical Society. 144 (41): 18756–18760. Bibcode:2022JAChS.14418756H. doi:10.1021/jacs.2c07913. PMC 10430604 Check |pmc= value (help). PMID 36201634 Check |pmid= value (help).
  20. ↑ Radovic-Moreno AF, Chernyak N, Mader CC, Nallagatla S, Kang RS, Hao L, et al. (March 31, 2015). "Immunomodulatory spherical nucleic acids". Proceedings of the National Academy of Sciences. 112 (13): 3892–7. doi:10.1136/jitc-2020-SITC2020.0423. PMID 25775582.
  21. ↑ Hwang J, Dittmar JW, Kang J, Ocampo T, Evangelopoulos M, Han Z, et al. (2024). "DNA Anchoring Strength Directly Correlates with Spherical Nucleic Acid–Based HPV E7 Cancer Vaccine Potency". Nano Letters. 24 (25): 7629–36. Bibcode:2024NanoL..24.7629H. doi:10.1021/acs.nanolett.4c01392. PMC 11540143 Check |pmc= value (help). PMID 38874796 Check |pmid= value (help).
  22. ↑ 22.0 22.1 Distler ME, Teplensky MH, Bujold KE, Kusmierz CD, Evangelopoulos M, Mirkin CA (2021). "DNA Dendrons as Agents for Intracellular Delivery". Journal of the American Chemical Society. 143 (34): 13513–18. Bibcode:2021JAChS.14313513D. doi:10.1021/jacs.1c07240. PMC 8582297 Check |pmc= value (help). PMID 34410116 Check |pmid= value (help).
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  24. ↑ Meng HM, Zhang X, Lv Y, Zhao Z, Wang NN, Fu T, et al. (2014). "DNA Dendrimer: An Efficient Nanocarrier of Functional Nucleic Acids for Intracellular Molecular Sensing". ACS Nano. 8 (6): 6171–81. Bibcode:2014ACSNa...8.6171M. doi:10.1021/nn5015962. PMC 4076030. PMID 24806614.
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  26. ↑ Samanta D, Ebrahimi SB, Kusmierz CD, Cheng HF, Mirkin CA (2020). "Protein Spherical Nucleic Acids for Live-Cell Chemical Analysis". Journal of the American Chemical Society. 142 (31): 13350–5. Bibcode:2020JAChS.14213350S. doi:10.1021/jacs.0c06866. PMC 7473486 Check |pmc= value (help). PMID 32706250 Check |pmid= value (help).
  27. ↑ Dosta P, Cryer AM, Dion MZ, Shiraishi T, Langston SP, Lok D, et al. (2023). "Investigation of the enhanced antitumour potency of STING agonist after conjugation to polymer nanoparticles". Nature Nanotechnology. 18 (11): 1351–63. Bibcode:2023NatNa..18.1351D. doi:10.1038/s41565-023-01447-7. PMID 37443252 Check |pmid= value (help).
  28. ↑ Oliva N, Conde J, Wang K, Artzi N (2017). "Designing Hydrogels for On-Demand Therapy". Accounts of Chemical Research. 50 (4): 669–79. doi:10.1021/acs.accounts.6b00536. PMC 6527116 Check |pmc= value (help). PMID 28301139.
  29. ↑ Winegar PH, Figg CA, Teplensky MH, Ramani N, Mirkin CA (2022). "Modular Nucleic Acid Scaffolds for Synthesizing Monodisperse and Sequence-Encoded Antibody Oligomers". Chem. 8 (11): 3018–30. Bibcode:2022Chem....8.3018W. doi:10.1016/j.chempr.2022.07.003. PMC 9674055 Check |pmc= value (help). PMID 36405374 Check |pmid= value (help).
  30. ↑ 30.0 30.1 Modica JA, Iderzorig T, Mrksich M (2020). "Design and Synthesis of Megamolecule Mimics of a Therapeutic Antibody". Journal of the American Chemical Society. 142 (32): 13657–61. Bibcode:2020JAChS.14213657M. doi:10.1021/jacs.0c05093. PMC 8534297 Check |pmc= value (help). PMID 32706963 Check |pmid= value (help).
  31. ↑ Sridhar S, Modica JA, Sykora DJ, Berns EJ, Mrksich M (2024). "Synthesis and Activity of T-Cell Tumor-Directing MegaMolecules". Journal of the American Chemical Society. 146 (39): 26801–26807. Bibcode:2024JAChS.14626801S. doi:10.1021/jacs.4c07377. PMID 39167468 Check |pmid= value (help).
  32. ↑ Seeman NC (1982). "Nucleic acid junctions and lattices". Journal of Theoretical Biology. 99 (2): 237–47. Bibcode:1982JThBi..99..237S. doi:10.1016/0022-5193(82)90002-9. PMID 6188926.
  33. ↑ Seeman NC, Sleiman HF (2017). "DNA nanotechnology". Nature Reviews Materials. 3 (1). doi:10.1038/natrevmats.2017.68. Unknown parameter |article-number= ignored (help)
  34. ↑ Rothemund PW (2006). "Folding DNA to create nanoscale shapes and patterns". Nature. 440 (7082): 297–302. Bibcode:2006Natur.440..297R. doi:10.1038/nature04586. PMID 16541064.
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  36. ↑ Zeng YC, Young OJ, Wintersinger CM, Anastassacos FM, Macdonald JI, Isinelli G, et al. (2024). "Fine tuning of CpG spatial distribution with DNA origami for improved cancer vaccination". Nature Nanotechnology. 19 (7): 1055–65. Bibcode:2024NatNa..19.1055Z. doi:10.1038/s41565-024-01615-3. PMID 38491184 Check |pmid= value (help).
  37. ↑ Veneziano R, Moyer TJ, Stone MB, Wamhoff EC, Read BJ, Mukherjee S, et al. (2020). "Role of nanoscale antigen organization on B-cell activation probed using DNA origami". Nature Nanotechnology. 15 (8): 716–723. Bibcode:2020NatNa..15..716V. doi:10.1038/s41565-020-0719-0. PMC 7415668 Check |pmc= value (help). PMID 32601450 Check |pmid= value (help).


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