Metal–organic biohybrids (MOBs) are a family of materials containing a metal component, such as copper, and a biological component, such as the amino acid dimer cystine.[1] One of the MOB families first described was the copper-high aspect ratio structure called CuHARS. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) of CuHARS revealed linear morphology and smooth surface texture. SEM, TEM and light microscopy showed that CuHARS composites had scalable dimensions from nano- to micro-, with diameters as low as 40 nm, lengths exceeding 150 microns, and average aspect ratios of 100.[2]

Structure

MOBs are composed of two major components: a metal ion or cluster of metal ions and a biological molecule. Examples include CuHARS which contain copper as the metal ion and cystine as the biological molecule. Another example includes the use of silver as the metal ion in combination with cystine.[3] Cystine is the dimer form of the amino acid cysteine. Cobalt has also been used in combination with cystine to form CoMOBs.[4]

When combined with copper to form CuHARS, the cystine may provide a linker function leading to a linear, high-aspect ratio structure that gives CuHARS its name: copper high-aspect ratio structures. In contrast to CuHARS, MOBs formed with silver and cystine, result in silver nanoparticles with spherical, rounded structure. These have been named AgCysNPs.[3] Figure 1 shows comparative electron microscopy of CuHARS and AgCysNPs. [5]

Figure 1: Linear CuHARS (A) and AgCysNPs (B) are shown using scanning electron microscopy.






Synthesis

Synthesis: MOBs under reducing conditions using sodium hydroxide (NaOH), can be self-assembled at body temperature (37 degrees Celsius).[1] In the case of copper CuHARS, MOBs can be produced by transforming copper nanoparticles to provide the copper source, or by utilizing copper(II) sulfate. [1]

Physical Characteristics

CuHARS have been shown to completely degrade under physiological conditions (cell culture media at 37 °C), even in the absence of cells; this is possibly due to the metal chelating properties of typical cell culture medias.[6] These may include the copper-binding properties of cerulosplasmin [7] and of albumin.[8] Additionally, CuHARS have been shown to polarize light using inverted microscopy.[3] Cobalt-containing MOBs (CoMOBs) have been shown to be susceptible to an externally applied magnetic field as shown in Figure 2. [9]

Figure 2. Magnetic susceptibility of CoMOBs. Cobalt and copper containing MOBs were synthesized and exposed to a magnetic field




Uses and Applications

MOBs have been incorporated into composites including cellulose.[6] Additionally, MOBs composed of the copper-containing CuHARS have been shown to provide catalytic function[10] to produce nitric oxide (NO). 

    Nitric Oxide production:  This production of NO was shown to impart anti-microbial activity, and the CuHARS in this case were incorporated into a biodegradable, biocompatible, and renewable resource material, namely cellulose.[11]  The release of NO catalzyed by copper from CuHARS may have beneficial biomedical applications.[12]  
    Anti-Cancer Effects:  Both copper- and silver-containing MOBs were shown to have anti-cancer effect on cells in vitro.[3]  In the case of possible uses for CuHARS, copper may have a potential role in tumor immunity and for antitumor therapy.[13]  Since CuHARS are 100% biodegradable under physiological conditions,  copper metabolism of CuHARS may have benefits as an approach for treating glioma.[14]  
    MOBs as Green Materials using Self-Assembly:  Green nanomedicine has been suggested as a path to the next generation of materials for diagnosing brain tumors and for therapeutics, including the use of CuHARS.[15]

References

  1. 1 2 3 Cotton Kelly, Kinsey; Wasserman, Jessica R.; Deodhar, Sneha; Huckaby, Justin; Decoster, Mark A. (2015). "Generation of Scalable, Metallic High-Aspect Ratio Nanocomposites in a Biological Liquid Medium". Journal of Visualized Experiments (101): 52901. doi:10.3791/52901. PMC 4544365. PMID 26274773.
  2. ↑ Deodhar, Sneha; Huckaby, Justin; Delahoussaye, Miles; DeCoster, Mark A (22 August 2014). "High-Aspect Ratio Bio-Metallic Nanocomposites for Cellular Interactions". IOP Conference Series: Materials Science and Engineering. 64 (1): 012014. Bibcode:2014MS&E...64a2014D. doi:10.1088/1757-899X/64/1/012014. S2CID 136497427.
  3. 1 2 3 4 Karekar, Neha; Karan, Anik; Khezerlou, Elnaz; Prajapati, Neela; Pernici, Chelsea D.; Murray, Teresa A.; Decoster, Mark A. (2019). "Self-Assembled Metal–Organic Biohybrids (MOBs) Using Copper and Silver for Cell Studies". Nanomaterials. 9 (9): 1282. doi:10.3390/nano9091282. PMC 6781094. PMID 31500351.
  4. ↑ Uppu, N., McMahen, K., Khasru, T. and DeCoster, M., 2022. Green Synthesis of Metal-Organic Biohybrid (Mob) Nanomaterials. Recent Progress in Materials, 4(4), pp.1-14. https://www.lidsen.com/journals/rpm/rpm-04-04-020
  5. ↑ Prajapati, N., Karan, A., Khezerlou, E. and DeCoster, M.A., 2021. The immunomodulatory potential of copper and silver based self-assembled metal organic biohybrids nanomaterials in cancer theranostics. Frontiers in chemistry, 8, p.629835.
  6. 1 2 Karan, Anik; Darder, Margarita; Kansakar, Urna; Norcross, Zach; DeCoster, Mark A. (May 2018). "Integration of a Copper-Containing Biohybrid (CuHARS) with Cellulose for Subsequent Degradation and Biomedical Control". International Journal of Environmental Research and Public Health. 15 (5): 844. doi:10.3390/ijerph15050844. PMC 5981883. PMID 29693569.
  7. ↑ Hellman, N.E. and Gitlin, J.D., 2002. Ceruloplasmin metabolism and function. Annual review of nutrition, 22(1), pp.439-458.
  8. ↑ Løvstad, R.A., 2004. A kinetic study on the distribution of Cu (II)-ions between albumin and transferrin. BioMetals, 17, pp.111-113.
  9. ↑ Uppu, N., McMahen, K., Khasru, T. and DeCoster, M., 2022. Green Synthesis of Metal-Organic Biohybrid (Mob) Nanomaterials. Recent Progress in Materials, 4(4), pp.1-14.
  10. ↑ Darder, Margarita; Karan, Anik; Real, Gustavo del; DeCoster, Mark A. (March 2020). "Cellulose-based biomaterials integrated with copper-cystine hybrid structures as catalysts for nitric oxide generation". Materials Science and Engineering: C. 108: 110369. doi:10.1016/j.msec.2019.110369. hdl:10261/331060. PMID 31923961. S2CID 209706898.
  11. ↑ Seabra, A.B., Silveira, N.M., Ribeiro, R.V., Pieretti, J.C., Barroso, J.B., Corpas, F.J., Palma, J.M., Hancock, J.T., Petřivalský, M., Gupta, K.J. and Wendehenne, D., 2022. Nitric oxide-releasing nanomaterials: from basic research to potential biotechnological applications in agriculture. New Phytologist, 234(4), pp.1119-1125.
  12. ↑ Andrabi, S.M., Sharma, N.S., Karan, A., Shahriar, S.S., Cordon, B., Ma, B. and Xie, J., 2023. Nitric Oxide: Physiological Functions, Delivery, and Biomedical Applications. Advanced Science, 10(30), p.2303259.
  13. ↑ Song, Q., Zhou, R., Shu, F. and Fu, W., 2022. Cuproptosis scoring system to predict the clinical outcome and immune response in bladder cancer. Frontiers in immunology, 13, p.958368.
  14. ↑ Cazzoli, R., Zamborlin, A., Ermini, M.L., Salerno, A., Curcio, M., Nicoletta, F.P., Iemma, F., Vittorio, O., Voliani, V. and Cirillo, G., 2023. Evolving approaches in glioma treatment: harnessing the potential of copper metabolism modulation. RSC advances, 13(48), pp.34045-34056.
  15. ↑ Mostafavi, E., Medina-Cruz, D., Vernet-Crua, A., Chen, J., Cholula-Diaz, J.L., Guisbiers, G. and Webster, T.J., 2021. Green nanomedicine: the path to the next generation of nanomaterials for diagnosing brain tumors and therapeutics?. Expert Opinion on Drug Delivery, 18(6), pp.715-736.

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