Abstract
The aim of the study was to evaluate percutaneous penetration of platinum and rhodium nanoparticles (PtNPs: 5.8 ± 0.9 nm, RhNPs: 5.3 ± 1.9 nm) through human skin. Salts compounds of these metals are sensitizers and some also carcinogenic agents. In vitro permeation experiments were performed using Franz diffusion cells with intact and damaged skin. PtNPs and RhNPs, stabilized with polyvinylpyrrolidone, were synthesized by reduction of Na2PtCl6 and RhCl3·3H2O respectively. Suspensions with a concentration of 2.0 g/L of PtNPs and RhNPs were dispersed separately in synthetic sweat at pH 4.5 and applied as donor phases to the outer surface of the skin for 24 h. Measurements of the content of the metals in the receiving solution and in the skin were performed subsequently. Rhodium skin permeation was demonstrated through damaged skin, with a permeation flux of 0.04 ± 0.04 μg cm−2 h−1 and a lag time of 7.9 ± 1.1 h, while no traces of platinum were found in receiving solutions. Platinum and rhodium skin-analysis showed significantly higher concentrations of the metals in damaged skin. Rh and Pt applied as NPs can penetrate the skin barrier and Rh can be found in receiving solutions. These experiments pointed out the need for skin contamination prevention, since even a minor injury to the skin barrier can significantly increase penetration.
Similar content being viewed by others
References
Barbante C, Veysseyre A, Ferrari C, van de Velde K, Morel C, Capodaglio G, Cescon P, Scarponi G, Boutron C (2001) Greenland snow evidence of large scale atmospheric contamination for platinum, palladium and rhodium. Environ Sci Technol 35:835–839
Baroli B (2010) Penetration of nanoparticles and nanomaterials in the skin: fiction or reality? J Pharm Sci 99:21–50
Birchall J, Coulman S, Anstey A, Gateley C, Sweetland H, Gershonowitz A, Neville L, Levin G (2006) Cutaneous gene expression of plasmid DNA in excised human skin following delivery via microchannels created by radio frequency ablation. Int J Pharm 312(1–2):15–23
Blosi M, Albonetti S, Dondi M, Martelli C, Baldi G (2011) Microwave-assisted polyol synthesis of Cu nanoparticles. J Nanopart Res 13:127–138
Blosi M, Albonetti S, Ortelli S, Costa AL, Ortolani L, Dondi M (2014) Green and easily scalable microwave synthesis of noble metal nanosols (Au, Ag, Cu, Pd) usable as catalysts. New J Chem 38:1401–1409
Bocca B, Caimi S, Smichowski P, Gómez D, Caroli S (2006) Monitoring Pt and Rh in urban aerosols from Buenos Aires, Argentina. Sci Total Environ 358(1–3):255–264
Bronaugh RL, Steward RF (1985) Methods for in vitro percutaneous absorption studies V: permeation through damaged skin. J Pharm Sci 74:1062–1066
Brubaker PE, Moran JP, Bridbord K, Hueter FG (1975) Noble metals: a toxicological appraisal of potential new environmental contaminants. Environ Health Perspect 10:39–56
Bünger J, Stork J, Stalder K (1996) Cyto and genotoxic effects of coordination complexes of platinum, palladium and rhodium in vitro. Int Arch Occup Environ Health 69(1):33–38
Carneiro ML, Nunes ES, Peixoto RC, Oliveira RG, Lourenço LH, da Silva IC, Simioni AR, Tedesco AC, de Souza AR, Lacava ZG, Báo SN (2011) Free Rhodium (II) citrate and rhodium (II) citrate magnetic carriers as potential strategies for breast cancer therapy. J Nanobiotechnol. doi:10.1186/1477-3155-9-11
Colombo C, Monhemius AJ, Plant JA (2008a) The estimation of the bioavailabilities of platinum, palladium and rhodium in vehicle exhaust catalysts and road dusts using a physiologically based extraction test. Sci Total Environ 389(1):46–51
Colombo C, Monhemius AJ, Plant JA (2008b) Platinum, palladium and rhodium release from vehicle exhaust catalysts and road dust exposed to simulated lung fluids. Ecotoxicol Environ Saf 71(3):722–730
Cristaudo A, Sera F, Severino V, De Rocco M, Di Lella E, Picardo M (2005) Occupational hypersensitivity to metal salts, including platinum, in the secondary industry. Allergy 60(2):159–164
Davies DJ, Ward RJ, Heylings JR (2004) Multi-species assessment of electrical resistance as a skin integrity marker for in vitro percutaneous absorption studies. Toxicol In Vitro 18(3):351–358
EDETOX Evaluations and predictions of dermal absorption of toxic chemicals (2001–2004) QLK4-CT-2000-00196. www.edetox.ncl.ac.uk
Fasano WJ, Manning LA, Green JW (2002) Rapid assessment of rat and human epidermal membranes for in vitro dermal regulatory testing: correlation of electrical resistance with tritiated water permeability. Toxicol In Vitro 16(6):731–740
Forte G, Petrucci F, Bocca B (2008) Metal allergens of growing significance: epidemiology, immunotoxicology, strategies for testing and prevention. Inflamm Allergy Drug Targets 7(3):145–162
Franken A, Eloff FC, Du Plessis J, Badenhorst J, Jordaan A, Du Plessis L (2014) In vitro permeation of platinum and rhodium through caucasian skin. Toxicol In Vitro 28(8):1396–1401
Franz TJ (1975) Percutaneous absorption. On the relevance of in vitro data. J Investig Dermatol 93:633–640
Fuchs WA, Rose AW (1974) Geochemical behavior of platinum and palladium in the weathering cycle in the stillwater complex. Montana Econ Geol 69:332–346
Gebel T, Lantzsch H, Plessow K, Dunkelberg H (1997) Genotoxicity of platinum and palladium compounds in human and bacterial cells. Mutat Res 389(2–3):183–190
Goossens A, Cattaert N, Nemery B, Boey L, De Graef E (2011) Occupational contact dermatitis caused by rhodium solutions. Contact Dermat 64(3):158–161
Health and Safety Executive (1990) Occupational exposure limits. Guidance note EH 40910. London: Her Majestry’s Stationary Office
Hunter D, Milton R, Perry KMA (1945) Asthma caused by the complex salts of platinum. Br J Ind Med 2(2):92–98
Iavicoli I, Cufino V, Corbi M, Goracci M, Caredda E, Cittadini A, Bergamaschi A, Sgambato A (2012) Rhodium and iridium salts inhibit proliferation and induce DNA damage in rat fibroblasts in vitro. Toxicol In Vitro 26(6):963–969
Kajita M, Hikosaka K, Iitsuka M, Kanayama A, Toshima N, Miyamoto Y (2007) Platinum nanoparticle is a useful scavenger of superoxide anion and hydrogen peroxide. Free Radical Res 41(6):615–626
Konieczny P, Goralczyk AG, Szmyd R, Skalniak L, Koziel J, Larese FF, Crosera M, Cierniak A, Zuba-Surma EK, Borowczyk J, Laczna E, Drukala J, Pyza E, Semik D, Woznicka O, Klein A, Jura J (2013) Effects triggered by platinum nanoparticles on primary keratinocytes. Int J Nanomed 8:3963–3975
Larese FF, D’Agostin F, Crosera M, Adami G, Bovenzi M, Maina G (2008) In vitro percutaneous absorption of chromium powder and the effect of skin cleanser. Toxicol In Vitro 22(6):1562–1567
Larese FF, D’Agostin F, Crosera M, Adami G, Renzi N, Bovenzi M, Maina G (2009a) Human skin penetration of silver nanoparticles through intact and damaged skin. Toxicology 255(1–2):33–37
Larese FF, D’Agostin F, Crosera M, Adami G, Bovenzi M, Maina G (2009b) In vitro absorption of metal powders through intact and damaged skin. Toxicol In Vitro 23(4):574–579
Larese FF, Crosera M, Adami G, Bovenzi M, Rossi F, Maina G (2011) Human skin penetration of gold nanoparticles through intact and damaged skin. Nanotoxicology 5(4):493–501
Larese FF, Crosera M, Timeus E, Adami G, Bovenzi M, Ponti J, Maina G (2013) Human skin penetration of cobalt nanoparticles through intact and damaged skin. Toxicol In Vitro 27(1):121–127
Linett PJ, Hughes EG (1999) 20 years of medical surveillance on exposure to allergenic and non allergenic platinum compounds: the importance of chemical speciation. Occup Environ Med 56(3):191–196
Merget R (2000) Occupational platinum salt allergy. Diagnosis, prognosis, prevention and therapy. In: Zereini F, Alt F (eds) Anthropogenic platinum-group element emissions. Their impact on man and environment. Springer-Verlag, Berlin, p 32
Merget R, Rosner G (2001) Evaluation of the health risk of platinum group metals emitted from automotive catalytic converters. Sci Total Environ 270(1–3):165–173
Merget R, Sander I, van Kampen V, Raulf-Heimsoth M, Ulmer HM, Kulzer R, Bruening T (2010) Occupational immediate-type asthma and rhinitis due to rhodium salts. Am J Ind Med 53(1):42–46
Moldovan M, Palacios MA, Gòmez MM, Morrison G, Rauch S, McLeod C, Ma R, Caroli S, Alimonti A, Petrucci F, Bocca B, Schramel P, Zischka M, Pettersson C, Wass U, Luna M, Saenz JC, Santamaría J (2002) Environmental risk of particulate and soluble platinum group elements released from gasoline and diesel engine catalytic converters. Sci Total Environ 296(1–3):199–208
Murdoch RD, Pepys J (1987) Platinum group metal sensitivity: reactivity to platinum group metal salts in platinum halide salt-sensitive workers. Ann Allergy 59(6):464–469
Nakayama H, Ichikawa T (1997) Occupational contact urticaria syndrome due to rhodium and platinum. In: Amin S, Maibach HI, Lahti S (eds) Contact urticaria syndrome. CRC Press, New York, pp 233–240
Niezborala M, Garnier R (1996) Allergy to complex platinum salts: a historical prospective cohort study. Occup Environ Med 53(4):252–257
Onizawa S, Aoshiba K, Kajita M, Miyamoto Y, Nagai A (2009) Platinum nanoparticle antioxidants inhibit pulmonary inflammation in mice exposed to cigarette smoke. Pulm Pharmacol Ther 22(4):340–349
Orbaek P (1982) Allergy to the complex salts of platinum, A review of the literature and three case reports. Scand J Work Environ Health 8(2):141–145
Peng Choo H, Yong Liew K, Liu H (2002) Factors affecting the size of polymer stabilized Pd nanoparticles. J Mater Chem 12:934–937
Rancan F, Gao Q, Graf C, Troppens S, Hadam S, Vogt A (2012) Skin penetration and cellular uptake of amorphous silica nanoparticles with variable size, surface functionalization and colloidal stability. ACS Nano 8:6829–6842
Ravindra K, Bencs L, Van Grieken R (2004) Platinum group elements in the environment and their health risk. Sci Total Environ 318(1–3):1–43
Roshchin AV, Veselov VG, Panova AI (1984) lndustrial toxicology of metals of the platinum group. J Hyg Epidemiol Microbiol Immunol 28:17–24
Santucci B, Valenzano C, de Rocco M, Cristaudo A (2000) Platinum in the environment: frequency of reactions to platinum-group elements in patients with dermatitis and urticaria. Contact Dermat 43(6):333–338
Schierl R (2000) Environmental monitoring of platinum in air and urine. Microchem J 67:245–248
Taubler J (1977) Allergic response to platinum and palladium complexes. Determination of no-effect level. US Environmental Protection Agency, North Carolina, EPA-600/1-77-039,NTIS Accession Number PB 271 659, p 81
WHO (1991) Environmental Health Criteria 125—Platinum. International Programme on Chemical Safety, Geneva
Yoshihisa Y, Honda A, Zhao QL, Makino T, Abe R, Matsui K, Shimizu H, Miyamoto Y, Kondo T, Shimizu T (2010) Protective effects of platinum nanoparticles against UV-light induced epidermal inflammation. Exp Dermatol 19(11):1000–1006
Zereini F, Skerstrupp B, Alt F, Helmers E, Urban H (1997) Geochemical behavior of platinum group elements (PGE) in particulate emissions by automobile exhaust catalysts: experimental results and environmental investigations. Sci Total Environ 206:137–146
Zhang W, Gao J, Zhu Q, Zhang M, Ding X, Wang X, Hou X, Fan W, Ding B, Wu X, Wang X, Gao S (2010) Penetration and distribution of PLGA nanoparticles in the human skin treated with microneedles. Int J Pharm 402:205–212
Acknowledgments
The authors acknowledge the financial support of FRA 2009 and 2012 from University of Trieste and of Cost Action Skinbad BM 0903. MICROMERITICS Analytical Service is kindly acknowledged for DLS analysis.
Conflict of interest
The authors declare that they have no conflict of interest.
Author information
Authors and Affiliations
Corresponding author
Additional information
Marcella Mauro and Matteo Crosera have equally contributed to this work.
Rights and permissions
About this article
Cite this article
Mauro, M., Crosera, M., Bianco, C. et al. Permeation of platinum and rhodium nanoparticles through intact and damaged human skin. J Nanopart Res 17, 253 (2015). https://doi.org/10.1007/s11051-015-3052-z
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s11051-015-3052-z