Synthesis of novel PVA–starch formulation-supported Cu–Zn nanoparticle carrying carbon nanofibers as a nanofertilizer: controlled release of micronutrients

Biomaterials
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Abstract

Recent applications of nanotechnology in agriculture have successfully demonstrated the utility of nanomaterials as a potential plant-growth regulator. Practical application of nanomaterial-based fertilizers in agricultural lands requires a suitable substrate to effectively disperse the nanomaterials. In this study, a polymeric formulation of PVA–starch was synthesized as a substrate for the slow release of the Cu–Zn micronutrient carrying carbon nanofibers (CNFs). The Cu–Zn/CNFs were in situ dispersed in the PVA–starch blend during a polymerization step. The effectiveness of the prepared nanofertilizer was demonstrated using chickpea as a model plant and different doses, viz. 0.25, 0.50, 1.0, 2.0 and 4.0 g of PBMC per kg of soil (garden) up to 30 days. The dissolution of PBMC increased with increasing amounts of starch in the PBMC matrix, indicating the biodegradability of PVA in the blend. Scanning electron microscopy and elemental analysis confirmed the translocation of the Cu–Zn/CNFs from roots to shoots of the plant. The PBMC(1-1)-grown plants were measured to be the tallest (~ 33 cm), whereas the control plants reached a length of ~ 18 cm only, indicating the effectiveness of the prepared micronutrient in sustaining the plant growth. The superoxide anion radicals and hydrogen peroxide in the control plants were measured to be 207 ± 3.15 and 272 ± 5.74 nmol/g of the plant, whereas PBMC(1-1)-grown plants contained 129 ± 3.25 and 194 ± 6.47 nmol/g of the reactive oxygen species, respectively, indicating that the Zn nanoparticles were effective in scavenging the reactive species. The metal release profiles of PBMC indicated the Cu and Zn concentrations to be 5.3 ± 0.05 and 2.8 ± 0.1 mg/g-CNF, respectively, which were significantly lower from Cu–Zn/CNF, attributed to the slow release of the metals from the prepared polymeric formulation. The proposed integration of the biodegradable polymeric formulation with the micronutrient carrying CNFs opens a new perspective on the application of nanotechnology in agricultural practices.

Notes

Acknowledgements

The authors acknowledge the financial support received from the Council of Scientific & Industrial Research (CSIR) (New Delhi, India) in the form of a research grant (No: 9 22(4803)/14). The authors also acknowledge the provision of ACFs from Kynol Inc. (Tokyo, Japan).

Supplementary material

10853_2018_2107_MOESM1_ESM.docx (2.2 mb)
Supplementary material 1 (DOCX 2223 kb)

References

  1. 1.
    Alexander G, Katja K, Thomas DB (2012) Nanomaterials in plant protection and fertilization: current state, foreseen applications, and research priorities. J Agric Food Chem 60:9781–9792CrossRefGoogle Scholar
  2. 2.
    Zheng L, Hong F, Lu S, Liu C (2005) Effect of nano-TiO2 on spinach of naturally aged seeds and growth of spinach. Biol Trace Element Res 104:83–91CrossRefGoogle Scholar
  3. 3.
    Klaine SJ, Alvarez PJJ, Batley GE, Fernandes TF, Handry RD, Lyon DY, Manendra S, McKaughlin MJ, Lead JR (2008) Nanomaterials in the environment: behavior, fate bioavailability, and effects. Environ Toxicol Chem 27:1825–1851CrossRefGoogle Scholar
  4. 4.
    Laware S, Raskar S (2014) Influence of zinc oxide nanoparticles on growth, flowering and seed productivity in onion. Int J Curr Microbiol Appl Sci 3:874–881Google Scholar
  5. 5.
    Hafeez A, Razzaq A, Mahmood T, Jhanzab HM (2015) Potential of copper nanoparticles to increase growth and yield of wheat. J Nanosci Adv Technol 1:6–11Google Scholar
  6. 6.
    Mondal A, Basu R, Das S, Nandyet P (2011) Beneficial role of carbon nanotubes on mustard plant growth: an agricultural prospect. J Nanopart Res 13:4519–4528CrossRefGoogle Scholar
  7. 7.
    Khodakovskaya MV, De-Silva K, Nedosekin D, Dervishi E, Biris AS, Shashkov EV, Galanzha EI, Zharov VP (2011) Complex genetic, photothermal, and photoacoustic analysis of nanoparticle-plant interactions. Proc Natl Acad Sci USA 108:1028–1033CrossRefGoogle Scholar
  8. 8.
    Khodakovskaya MV, Kim BS, Kim JN, Alimohammadi M, Dervishi E, Mustafa T, Cernigla CE (2013) Carbon nanotubes as plant growth regulators: effects on tomato growth, reproductive system, and soil microbial community. Small 9:115–123CrossRefGoogle Scholar
  9. 9.
    Khodakovskaya MV, De-Silva K, Biris AS, Dervishi E, Villagarcia H (2012) Carbon nanotubes induce growth enhancement of tobacco cells. ACS Nano 3:2128–2135CrossRefGoogle Scholar
  10. 10.
    Ashfaq M, Verma N, Khan S (2017) Carbon nanofibers as a micronutrient carrier in plants: efficient translocation and controlled release of Cu nanoparticles. Environ Sci Nano 4:138–148CrossRefGoogle Scholar
  11. 11.
    Torney F, Trewyn BG, Lin VSY, Wang K (2007) Mesoporous silica nanoparticles deliver DNA and chemicals into plants. Nature Nano 2:295–300CrossRefGoogle Scholar
  12. 12.
    Liu Q, Chen B, Wang Q, Shi X, Xiao Z, Lin J, Fang X (2009) Carbon nanotubes as molecular transporters for walled plant cells. Nano Lett 9:1007–1010CrossRefGoogle Scholar
  13. 13.
    Davern SM, McKnight TE, Standaert RF, Morrell-Falvey JL, Shpak ED, Kalluri UC, Jelenska J, Greenberg JT, Mirzadeh S (2016) Carbon nanofiber arrays: a novel tool for microdelivery of biomolecules to plants. PLoS ONE 11:e0153621CrossRefGoogle Scholar
  14. 14.
    De La Torre-Roche R, Hawthorne J, Deng Y, Xing B, Cai W, Newman LA, Wang Q, Ma X, Hamdi H, White JC (2013) Multiwalled carbon nanotubes and C60 fullerenes differentially impact the accumulation of weathered pesticides in four agricultural plants. Environ Sci Technol 47:12539–12547CrossRefGoogle Scholar
  15. 15.
    Song U, Jun H, Waldman B, Roh J, Kim Y, Yi J, Lee EJ (2013) Functional analyses of nanoparticle toxicity: a comparative study of the effects of TiO2 and Ag on tomatoes (Lycopersicon esculentum). Ecotoxicol Environ Saf 93:60–67CrossRefGoogle Scholar
  16. 16.
    Sabo-Attwood T, Unrine JM, Stone JW, Murphy CJ, Ghoshroy S, Blom D, Bertsch PM, Newman LA (2012) Uptake, distribution and toxicity of gold nanoparticles in tobacco (Nicotiana xanthi) seedlings. Nanotoxicology. 6:353–360CrossRefGoogle Scholar
  17. 17.
    Tomaszewska M, Jarosiewicz A (2002) Use of polysulfone in controlled-release NPK fertilizer formulations. J Agric Food Chem 50:4634–4639CrossRefGoogle Scholar
  18. 18.
    Jarosiewicz A, Tomaszewska M (2003) Controlled-release NPK fertilizer encapsulated by polymeric membranes. J Agric Food Chem 51:413–417CrossRefGoogle Scholar
  19. 19.
    Wu L, Liu M (2008) Preparation and properties of chitosan-coated NPK compound fertilizer with controlled-release and water-retention. Carbohydr Polym 72:240–247CrossRefGoogle Scholar
  20. 20.
    De-Campos Bernardi AC, Oliviera PP, De-Melo Monte MB, Souza-Barros F (2013) Brazilian sedimentary zeolite use in agriculture. Micropor Mesopor Mater 167:16–21CrossRefGoogle Scholar
  21. 21.
    Anstoetz M, Sharma N, Clark M, Yee LH (2016) Characterization of an oxalate-phosphate-amine metal-organic framework (OPA-MOF) exhibiting properties suited for innovative applications in agriculture. J Mater Sci 51:9239–9252.  https://doi.org/10.1007/s10853-016-0171-6 CrossRefGoogle Scholar
  22. 22.
    Ray SK, Varadachari C, Ghosh K (1997) Novel slow-releasing micronutrient fertilizers. 2. Copper compounds. J Agric Food Chem. 45:1447–1453CrossRefGoogle Scholar
  23. 23.
    Chandra PK, Ghosh K, Varadachari C (2009) A new slow-releasing iron fertilizer. Chem Eng J 155:451–456CrossRefGoogle Scholar
  24. 24.
    Bin Hussein MZ, Zainal Z, Yahaya AH, Foo DW (2002) Controlled release of a plant growth regulator, α-naphthaleneacetate from the lamella of Zn–Al-layered double hydroxide nanocomposite. J Control Release 82:417–427CrossRefGoogle Scholar
  25. 25.
    Quiñones JP, García YC, Curiel H, Covas CP (2010) Microspheres of chitosan for controlled delivery of brassinosteroids with biological activity as agrochemicals. Carbohydr Polym 80:915–921CrossRefGoogle Scholar
  26. 26.
    Malinconico M, Immirzi B (2002) Blends of polyvinylalcohol and functionalized polycaprolactone. A study on the melt extrusion and post-cure of films suitable for protected cultivation. J Mater Sci 37:4973–4978.  https://doi.org/10.1023/A:1021058810774 CrossRefGoogle Scholar
  27. 27.
    Tang X, Alavi S (2011) Recent advances in starch, polyvinyl alcohol based polymer blends, nanocomposites and their biodegradability. Carbohydr Polym 85:7–16CrossRefGoogle Scholar
  28. 28.
    Marschner H (1995) Mineral nutrition of higher plants, 2nd edn. Academic Press, LondonGoogle Scholar
  29. 29.
    Singh A, Singh NB, Afzal S, Singh T, Hussain I (2018) Zinc oxide nanoparticles: a review of their biological synthesis, antimicrobial activity, uptake, translocation and biotransformation in plants. J Mater Sci 53:185–201.  https://doi.org/10.1007/s10853-017-1544-1 CrossRefGoogle Scholar
  30. 30.
    Ashfaq M, Singh S, Sharma A, Verma N (2013) Cytotoxic evaluation of the hierarchical web of carbon micronanofibers. Ind Eng Chem Res 52:4672–4682CrossRefGoogle Scholar
  31. 31.
    Ashfaq M, Verma N, Khan S (2016) Copper/zinc bimetal nanoparticles-dispersed carbon nanofibers: a novel potential antibiotic material. Mater Sci Eng C 59:938–947CrossRefGoogle Scholar
  32. 32.
    Ashfaq M, Khan S, Verma N (2014) Synthesis of PVA-CAP-based biomaterial in situ dispersed with Cu nanoparticles and carbon micro-nanofibers for antibiotic drug delivery applications. Biochem Eng J 90:79–89CrossRefGoogle Scholar
  33. 33.
    Ashfaq M, Verma N, Khan S (2017) Highly effective Cu/Zn-carbon micro/nanofiber-polymer nanocomposite-based wound dressing biomaterial against the P. aeruginosa multi- and extensively drug-resistant strains. Mater Sci Eng C 77:630–641CrossRefGoogle Scholar
  34. 34.
    Yew SP, Tang HY, Sudesh K (2006) Photocatalytic activity and biodegradation of polyhydroxybutyrate films containing titanium dioxide. Polym Degrad Stab 91:1800–1807CrossRefGoogle Scholar
  35. 35.
    Ni Z, Kim E, Ha M, Lackey E, Liu J, Zhang Y, Sun Q, Chen ZJ (2009) Altered circadian rhythms regulate growth vigour in hybrids and allopolyploids. Nature 457:327–333CrossRefGoogle Scholar
  36. 36.
    Lopez CVG, García MDCC, Fernández AGA, Bustos CS, Chisti Y, Sevilla JMF (2010) Protein measurements of microalgal and cyanobacterial biomass. Bioresour Technol 101:7587–7591CrossRefGoogle Scholar
  37. 37.
    Elstner EF, Heupel A (1976) Inhibition of nitrite formation from hydroxylammoniumchloride: a simple assay for superoxide dismutase. Anal Biochem 70:616–620CrossRefGoogle Scholar
  38. 38.
    Velikova V, Yordanov I, Edreva A (2000) Oxidative stress and some antioxidant systems in acid rain-treated bean plants: protective role of exogenous polyamines. Plant Sci 151:59–66CrossRefGoogle Scholar
  39. 39.
    Lin S, Reppert J, Hu Q, Hudson JS, Reid ML, Ratnikova TA, Rao AM, Luo H, Ke PC (2009) Uptake, translocation, and transmission of carbon nanomaterials in rice plants. Small 5:1128–1132CrossRefGoogle Scholar
  40. 40.
    Chichiriccò G, Poma A (2015) Penetration and toxicity of nanomaterials in higher plants. Nanomaterials 5:851–873CrossRefGoogle Scholar
  41. 41.
    Samreen T, Shah HU, Ullah S, Javid M (2013) Zinc effect on growth rate, chlorophyll, protein and mineral contents of hydroponically grown mungbeans plant (Vigna radiate L.). Arab J Chem 10:S1802–S1807CrossRefGoogle Scholar
  42. 42.
    Amaya I, Botella MA, de la Calle M, Medina MI, Heredia A, Bressan RA, Hasegawa PM, Quesada MA, Valpuesta V (1999) Improved germination under osmotic stress of tobacco plants overexpressing a cell wall peroxidase. FEBS Lett 457:80–84CrossRefGoogle Scholar
  43. 43.
    Turner AP (1994) The responses of plants to heavy metals. In: Ross SM (ed) Toxic metals in soil-plant systems. Wiley, Chichester, pp 153–187Google Scholar
  44. 44.
    Foyer CH, Harbinson J (1994) Oxygen metabolism and the regulation of photosynthetic electron transport. In: Foyer CH, Mullineaux P (eds) Causes of photooxidative stresses and amelioration of defense systems in plants. CRC Press, Boca Raton, pp 1–42Google Scholar
  45. 45.
    Del Rio LA, Sandalio LM, Corpas FJ, Palma JM, Barroso JB (2006) Reactive oxygen species and reactive nitrogen species in peroxisomes: production, scavenging, and role in cell signaling. Plant Physiol 141:330–335CrossRefGoogle Scholar
  46. 46.
    Begum P, Fugetsu B (2012) Phytotoxicity of multi-walled carbon nanotubes on red spinach (Amaranthus tricolor L.) and the role of ascorbic acid as an antioxidant. J Hazard Mater 243:212–222CrossRefGoogle Scholar
  47. 47.
    Da-Costa MVJ, Sharma PK (2016) Effect of copper oxide nanoparticles on growth, morphology, photosynthesis, and antioxidant response in Oryza sativa. Photosynthetica 54:110–119CrossRefGoogle Scholar
  48. 48.
    Kumari M, Khan SS, Pakrashi S, Mukherjee A, Chandrasekaran N (2011) Cytogenetic and genotoxic effects of zinc oxide nanoparticles on root cells of Allium cepa. J Hazard Mater 190:613–621CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Department of Chemical EngineeringIndian Institute of Technology KanpurKanpurIndia
  2. 2.School of Life SciencesBS Abdur Rahman Crescent Institute of Science and TechnologyChennaiIndia
  3. 3.Center for Environmental Science and EngineeringIndian Institute of Technology KanpurKanpurIndia

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