Nanoparticles can be modified with polymers and bioactive molecules aiming to achieve full efficiency in therapy and specific targeting. Polyhedral oligomeric silsesquioxane (POSS) is an organic-inorganic (RSiO1.5)8 hybrid material that consists of a –Si-O- inorganic core surrounded by tunable organic moieties. POSS is a highly symmetrical, cage-like structure, possible to add functional groups, both organic and inorganic in precision. POSS has been synthesized and characterized using FT-IR, ¹H NMR, EDAX, SEM, and TEM. It has been developed along with the thiol end group and paves a space for cross-linked nanostructures formation POSS-SH. Voids and spaces in the POSS cross-linked nanocarrier give enough space for drug loading up to 50 weight percentages. Here the therapy is done with the help of drug delivery application in an acidic medium found in the cancer cell site and acts as an internal trigger for drug release from POSS. The Presence of thiol end terminal has a greater affinity for attachment of gold which in turn provides an add-on application of photo dynamic therapy this combination is gold POSS- SH-Au. Cell viability studies proved that the POSS nanostructures are biocompatible. The developed POSS nanostructures can even be activated at acidic conditions, used for sustained release of drugs at specific targets, and provide in-vivo stability until they reache the tumor site. The POSS-SH-Au resulted an improvement in aqueous stability as its chains have the tendency to wrap around the siloxane cage and prevent the water from getting close to the siloxane frameworks.

Keywords: POSS, Crosslinked POSS nanodrug carrier, Cancer drug delivery, Gold nanoparticles, Upconverting nanoparticles.

1. Ahmad Mehdi, Catherine Reye, Robert Corriu, From molecular chemistry to hybrid Design and functionalization. Journal of chemical society reviews, 2; 2011.
2. Clement Sanchez, Philippe Belleville, Michael Popall, Lionel Nicole, Applications of advanced hybrid organic–inorganic nanomaterials: from laboratory to market, Journal of Chemical Society Reviews, 2, 2011.
3. Xin Du, Bingyang Shi, Ji Liang, Jingxu Bi, Sheng Dai, Shi Zhang Qiao, Developing Functionalized Dendrimer‐Like Silica Nanoparticles with Hierarchical Pores as Advanced Delivery Nanocarriers, 25, 2013; 5981-5985.
4. Takuya Iwamoto, Clinical application of drug delivery systems in cancer chemotherapy: review of the efficacy and side effects of approved drugs, Biological and Pharmaceutical Bulletin, 5,
5. Nair, B. P., Vaikkath, D., & Nair, P. D. (2013). Polyhedral oligomeric silsesquioxane-F68 hybrid vesicles for folate receptor targeted anti-cancer drug Langmuir, 30(1), 340- 347
6. Tanaka K, Jeon J H, Inafuku, K, and Chujo Y (2012) Enhancement of optical properties of dyes for bioprobes by freezing effect of molecular motion using POSS-core Bioorganic & medicinal chemistry, 20(2), 915-919.
7. Zhou H, Ye Q, and Xu J (2017) Polyhedral oligomeric silsesquioxane-based hybrid materials and their Materials Chemistry Frontiers, 1(2), 212-230.
8. Surface Modification of Gold Nanoparticles with Polyhedral Oligomeric Silsesquioxane and Incorporation within Polymer Matrices Shiao-Wei Kuo, Yung-Chien Wu,Chu-Hua Lu, Feng-Chih Chang, Wiley InterScience, DOI: 1002/polb.21686
9. Phillips S H, Haddad T S, and Tomczak S J (2004) Developments in nanoscience: polyhedral oligomeric silsesquioxane (POSS)-polymers. Current Opinion in Solid State and Materials Science, 8(1), 21-29.
10. McCusker C, Carroll J B and Rotello V M (2005) Cationic polyhedral oligomeric silsesquioxane (POSS) units as carriers for drug delivery Chemical Communications, (8), 996-998.
11. Chen K B, Chang Y P, Yang S H, and Hsu C S (2006) Novel dendritic light-emitting materials containing polyhedral oligomeric silsesquioxanes core. Thin Solid Films, 514(1- 2), 103-109.
12. Sheikh F A, Barakat N A, Kim B S, Aryal S, Khil M S, and Kim H Y (2009) Self-assembled amphiphilic polyhedral oligosilsesquioxane (POSS) grafted poly (vinyl alcohol) (PVA) Materials Science and Engineering: C, 29(3), 869-876.
13. Kim K O, Kim B S, and Kim, I S (2011) Self-Assembled Core-Shell Poly (Ethylene Glycol)-POSS Nanocarriers for Drug Journal of Biomaterials and Nanobiotechnology, 2(3), 201-206.
14. Pu Y, Chang S, Yuan H, Wang G, He B, and Gu Z (2013) The anti-tumor efficiency of poly (L-glutamic  acid) dendrimers    with     polyhedral     oligomeric     silsesquioxane Biomaterials, 34(14), 3658-3666.
15. Yang, Y., Wang, X., Hu, Y., Hu, H., Wu, D. C., & Xu, F. J. (2013) Bioreducible POSS-cored star-shaped polycation for efficient gene delivery. ACS applied materials & interfaces, 6(2), 1044-1052.
16. Gandhi S, Kumar P, Thandavan K, Jang K, Shin D S, and Vinu A (2014 Synthesis of a novel hierarchical mesoporous organic–inorganic nanohybrid using polyhedral oligomericsilsesquioxane New Journal of Chemistry, 38(7), 2766-2769.
17. Wang X, Yang Y, Gao P, Li D, Yang F, Shen H and Wu D (2014) POSS dendrimers constructed from a 1→ 7 branching monomer. Chemical communications, 50(46), 6126- 6129.
18. Teng C P, Mya K Y, Win K Y, Yeo C C,Low M, He C, and Han M Y (2014) Star-shaped polyhedral oligomeric silsesquioxane-polycaprolactone-polyurethane as biomaterials for tissue engineering NPG Asia Materials, 6(11), e142.
19. Abdulmajeed Almutary, (2017) Toxicity of four novel Polyhedral Oligomeric Silsesquioxane (POSS) particles used in anti- cancer drug delivery. Journal of Applied Pharmaceutical Science 7 (02), pp. 101-105.
20. Mosmann T., Rapid colorimetric assay for cellular growth and survival: application to proliferation and cytotoxicity Journal of immunological methods, 1983; 65, 55-63
21. Salata V, Applications of nanoparticles in biology and medicine. Journal of nanobiotechnology, 2004; 2, 1.
22. Neyertz S,Brown D, Pilz M, Rival N, Arstad B, Mannle F, and Simon C(2015) The stability of amino-functionalized polyhedral oligomeric silsesquioxanes in water. The Journal of Physical Chemistry B, 119(21), 6433-6447.
23. Piorecka K, Radzikowska E, Kurjata J, RozgaWijas K, Stanczyk W A, and Wielgus E (2016) Synthesis of the first POSS cage–anthracycline conjugates via amide bonds. New Journal of Chemistry, 40(7), 5997-6000.
24. Q Li, L Sun, W Zhou Z and Huang Y (2016) Dual stimuli-responsive hybrid polymeric nanoparticles self-assembled from POSS-based starlike copolymer-drug conjugates for efficient intracellular delivery of hydrophobic ACS applied materials & interfaces, 8(21), 13251-13261.
25. Pramudya I, Rico C G, Lee C, and Chung H (2016) POSS-containing bioinspired adhesives with  enhanced    mechanical    and    optical    properties     for     biomedical Biomacromolecules, 17(12), 3853-3861.
26. Narikiyo H, Kakuta T, Matsuyama H, Gon M, Tanaka K, and Chujo Y (2017) Development of the optical sensor for discriminating isomers of fatty acids based on emissive network polymers composed of polyhedral oligomeric Bioorganic & medicinal chemistry, 25(13), 3431-3436.
27. Zhou H, Ye Q, and Xu J (2017) Polyhedral oligomeric silsesquioxane-based hybrid materials and their Materials Chemistry Frontiers, 1(2), 212-230.
28. Sha Ding, Yuejun Liu and Zhengjian Qi (June 2017) Facile Synthesis and Self-Assembly o Amphiphilic Polyether-Octafunctionalized Polyhedral Oligomeric Silsesquioxane via Thiol-Ene Click Polymers2017,9,251; doi:10.3390/polym907025.
29. Yung-Chien Wu, Chu-Hua Lu, Feng-Chih Chang (February 2009) Surface Modification of Gold Nanoparticles with Polyhedral Oligomeric Silsesquioxane and Incorporation within Polymer Polymer Physics, Vol. 47, 811–819 (2009) VVC 2009 Wiley Periodicals, Inc.
30. Idris, N. M., Gnanasammandhan, M. K., Zhang, J., Ho, P. C., Mahendran, R., & Zhang, Y. (2012). In vivo photodynamic therapy using upconversion nanoparticles as remote- controlled Nature medicine, 18(10), 1580.
31. Tian, , Ren, W., Yan, L., Jian, S., Gu, Z., Zho u, L., ... & Zhao, Y. (2013). Red‐Emitting Upconverting Nanoparticles for Photodynamic Therapy in Cancer Cells Under Near‐Infrared Excitation. Small, 9(11), 1929-1938.
32. Wen, H., Zhu, H., Chen, X., Hung, T. F., Wang, B., Zhu, G., & Wang, F. (2013). Upconverting near‐infrared light through energy management in core–shell–shell Angewandte Chemie International Edition, 52(50), 13419-13423.
33. Chen, G., Ohulchanskyy, T. Y., Kumar, R., Ågren, H., & Prasad, P. N. (2010). Ultrasmall monodisperse NaYF4: Yb3+/Tm3+ nanocrystals with enhanced near-infrared to near- infrared upconversion ACS nano, 4(6), 3163-3168.
34. Dai, Y., Xiao, H., Liu, J., Yuan, Q., Ma, P. A., Yang, D., & Lin, J. (2013). In vivo multimodality imaging and cancer therapy by near-infrared light-triggered trans-platinum pro-drug-conjugated upconverison Journal of the American Chemical Society, 135(50), 18920-18929.
35. Neyertz Brown D, Pilz M, Rival N, Arstad B, Mannle F, and Simon C(2015) The stability of amino-functionalized polyhedral oligomeric silsesquioxanes in water. The Journal of Physical Chemistry B, 119(21), 6433-6447.
36. Piorecka K, Radzikowska E, Kurjata J, RozgaWijas K, Stanczyk W A, and Wielgus E (2016) Synthesis of the first POSS cage–anthracycline conjugates via amide bonds. New Journal of Chemistry, 40(7), 5997-6000.
37. Q Li, L Sun, W Zhou Z and Huang Y (2016) Dual stimuli-responsive hybrid polymeric nanoparticles self-assembled from POSS-based starlike copolymer-drug conjugates for efficient intracellular delivery of hydrophobic ACS applied materials & interfaces, 8(21), 13251-13261.
38. Pramudya I, Rico C G, Lee C, and Chung H (2016) POSS-containing bioinspired adhesives with  enhanced    mechanical    and    optical    properties     for     biomedical Biomacromolecules, 17(12), 3853-3861.
39. Narikiyo H, Kakuta T, Matsuyama H, Gon M, Tanaka K, and Chujo Y(2017) Development of the optical sensor for discriminating isomers of fatty acids based on emissive network polymers composed of polyhedral oligomeric silsesquioxane. Bioorganic & medicinal chemistry, 25(13), 3431-3436.
40. Abiramee Ravi, Anusha Ponnusamy, Kirthika Krishnamoorthy, (2021) Preparation, Characterisation, In-Vitro Drug release and kinetics studies of Canaglifozin Polymeric nanoparticles, Journal of Medical science and clinical research JMSCR, 09, 06, Page 183-192.
41. Zhou H, Ye Q, and Xu J (2017) Polyhedral oligomeric silsesquioxane-based hybrid materials and their Materials Chemistry Frontiers, 1(2), 212-230.
42. Xue, Meng & Zhang, Xian & Wu, Zhaofeng & Wang, Huan & Ding, Xin & Tian, (2013). Preparation and Flame Retardancy of Polyurethane/POSS Nanocomposites. Chinese Journal of Chemical Physics. 26. 445-450. 10.1063/1674-0068/26/04/445-450.
43. Beganskienė, V. Sirutkaitis, M. Kurtinaitienė, R. Juškėnas, A. Kareiva, FTIR, TEM and NMR investigations of Stöber silica nanoparticles, Mater. Sci. (Medžiagotyra) 10 (2004) 287–290.
44. Yang, H. Xu, J. Wang, S. Gang, C. Li, Preparation and thermal property of hybrid nanocomposites by free radical copolymerization of styrene with octavinyl polyhedral oligomeric silsesquioxane, J. Appl. Polym. Sci. 106 (2007) 320–3.
45. Almutary, A., & Sanderson, B. J. S. (2016). The MTT and Crystal Violet Assays. International Journal of Toxicology, 35(4), 454–462. Doi:10.1177/1091581816648906

Jaikumar V

Department of Chemical Engineering, Sri Sivasubramaniya Nadar College of Engineering, Chennai, India