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A Review of Iron polyphenol green nanomaterials and their environmental applications

DOI : https://doi.org/10.5281/zenodo.18296294
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A Review of Iron polyphenol green nanomaterials and their environmental applications

Jinat Aktar

Center for the Environment

Indian Institute of Technology Guwahati, Guwahati, Assam, India 781039

Abstract – Ironpolyphenol green nanomaterials have evolved as a promising class of sustainable materials due to its low toxicity, ecofriendly, and low-cost characteristics. This review investigates the synthesis, characterization, and prospective environmental implications of ironplant polyphenol complexes, with precise prominence on their function as green nanomaterials. Polyphenols developed from plant sources such phenolic acids act as natural antioxidant, and stabilizing agents, allowing formation of iron-based nanostructures under mild and environment friendly conditions. The review also enlightens the basic mechanisms governing ironpolyphenol complexation, including redox interactions, coordination reactions, and antioxidant activity, which mutually control material stability and reactivity.

Moreover, the review also imparts special focus on environmental applications, especially in wastewater treatments, where such nanomaterials validate high efficacy for remediation from heavy metals, dyes, nutrients, and even emerging contaminants through adsorption, and redox transformation. Their versatility goes beyond water treatment to beneficial agricultural applications, where ironpolyphenol complexes enhance bioavailability of micronutrient, soil health, and plant stress resistance. Furthermore, the intrinsic antimicrobial properties of polyphenols, synergistically improves by iron- mediated reactive oxygen species production, are reviewed in the context of bacterial resistance by damaging their cells.

Conclusively, this review highlights the prospectives of iron polyphenol green nanomaterials as economical, biodegradable, and scalable substitutes to conventional synthetic nanomaterials. Current challenges, knowledge gaps, and future research directions related to material optimization, environmental fate, and large-scale implementation are also discussed to facilitate their transition from laboratory research to real-world applications.

Keywords – Adsorption, green synthesis, iron polyphenol, pollutant removal, antimicrobial activity.

  1. INTRODUCTION

    In the twenty-first century, the worlds population is confronted with serious water quality challenges. Despite the fact that water is the most vital natural resource, just 1% of it is suitable for human use [1]. Approximately 1.1 billion people do not have access to safe drinking water, according to the World Health Organization (WHO, 2015). The water issue is exacerbated by poor water management, the generation of a massive volume of hazardous waste, and its improper disposal [2]. The inevitability of wastewater treatment reinforces the need to develop sustainable treatment options. Pollutants released in wastewater can be hazardous to aquatic life and able to change the condition of the aquatic ecosystem [3]. Various approaches for purifying wastewater have been developed, such as sedimentation, membrane filtration, flotation, precipitation, adsorption, ion exchange coagulation, oxidation, etc. [46]. Among them, adsorption is a much simpler and attractive procedure in comparison to other methods due to its high efficiency and ease of handling. Besides, it shows good efficiency in low concentrations of pollutants. Traditional methods for removing contaminants from wastewater are not cost- effective, particularly at low pollutant concentrations [7]. Moreover, adsorption has also been in practice for decades in the treatment of wastewater from distinct sources [810]. Additional benefits include the recovery of pure metal for recycling and the reuse of the adsorbent [11]. However, conventional adsorbents are chemically modified, susceptible to secondary effects, and expensive. Therefore, in the current scenario, there is an obvious need for sustainable, cost-effective, energy-efficient, and green adsorbent. This review is an attempt towards contributing to the water treatment process using eco-friendly efficient bio- adsorbent.

    Adsorption by biomaterials, commonly known as biosorption, is a popular approach where different parts of plants, dry leaves, shoot powder, barks, agricultural wastes, fruit shells, and a variety of other biological materials have all been investigated over the years (Figure.1) (Table 1.1).

    Activated carbon from coconut coil Eichhornia crassipes (Water hyacinth)

    Methylene blue [15]

    Phosphorus [16]

    Water hyacinth was modified by citric acid

    Ni (II), Cu (II), and Cr (VI)

    [17]

    Bamboo dust carbon Methylene blue [18]

    Tea extract mediated nanoparticles

    Malachite green, rhodamine B

    [19]

    Figure 1. Schematic representation of green synthesis of nanoparticles

    Bio-adsorbents have been the subject of a recent flurry of research articles due to their simple process, biodegradability, low cost, nontoxic, ecofriendly, and year-round availability. Some of the selected bio-absorbents used for the removal of different kinds of pollutants from wastewater are enlisted in the following table.

    Table 1.1. Selected list of different bio-adsorbent used in

    pollutant removal.

    Adsorbent Pollutant References

    Rice hull ash Lead (II) [1] NaOH treated rice husk Malachite green [2]

    Wheat bran Chromium (VI) [3]

    It can be concluded from the above table that different parts of plants, different agro-waste, water hyacinth, etc., in dry or powder form, in some modified form, after converting in charcoal were used for adsorption of different heavy metals, dyes, and other pollutants present in wastewater. However, in many literatures activated charcoal from different biomaterials were used for water treatment purposes but, energy consumption and air pollution is an adverse side of it. The use of biomaterials extract and different precursor salts for the synthesis of different metal-ligand complexes is another well- known area of study regarding environmental application and environmental chemistry.

    The presence of polyphenol in different parts of plants like root [29], shoot, leaves, seed [30], bulk, etc., acts as a ligand and makes complexation in the presence of different precursor metal salts. The specific components that cause plant-mediated metal complex synthesis and the mechanism of action are still unknown. Different secondary metabolites such as flavonoids, polyphenols, terpenoids, and heterocyclic compounds have been suggested to react with metal salts and produce plant mediated-metal complex [31,32]. Different polyphenols like gallic acid, ellagic acid, quercetin catechol derivatives etc., present in plant extracts are soluble in water, and some organic solvents react with precursor iron salt solutions (Figure 2).

    Polyphenols are chemically interesting due to their redox activity, which is the origin of their function as an antioxidant.

    Ocimum americanum L. seed pods

    Aegle marmelos correa

    (Bael fruit) Okra, pumpkin, grape,

    and squash

    Chromium (VI) [4]

    Chromium (VI) [5]

    Copper ions [6]

    Polyphenols are structurally diverse, and their reactivity depends on pH. The size distribution of these synthesized materials usually belongs within nano ranges [28,33,34]. Due to their high surface-to-volume ratio, nanoparticles are well known for their application in water treatment.

    Sugarcane bagasse Cu2+, Cd2+, and Pb2+ [7]

    Sugarcane bagasse Rhodamine B (RhB) andBasic Blue 9

    [8]

    Iron oxyhydroxide NP coated rice husk Azadirachta indica (Neem)

    Fluoride [9]

    Lead (II) [10]

    Rambutan peel based activated carbon

    Remazol Brilliant Blue R

    [11]

    Phoenix tree leaf powder Methylene blue [12] Pea peels Bismarck brown [13]

    Coconut husk Mercury (Hg0) [14]

    silver
    Stemona Gold 4-nitrophenol, [25]
    tuberosa Lour methylene blue,
    methyl orange and
    methyl red
    Lagerstroemia Leaf Gold methyl orange, [26]
    speciosa bromophenol blue
    and bromocresol
    green, and 4-
    nitropheno
    Hibiscus Flower Copper Nitrate [27]
    sabdariffa
    Citrofortunella Leaf Copper Rhodamin B [28]
    microcarpa
    Moringa Leaf Iron Nitrate removal, [29]
    oleifera
    Dodonaea Leaf Iron Antimicrobial [30]
    viscosa
    Laurus nobilis Leaf Iron Antimicrobial [31]
    L against Listeria
    monocytogenes
    bacterium.
    Carica papaya Leaf Iron Remazol yellow [32]
    RR dye
    degradation

    Figure 2. Structure of selected plant polyphenols.

    Tea Leaf Iron Malachite green,

    rhodamine B and methylene blue dye removal

    [19]

    Hence, these materials are also well known as green synthesized nanoparticles. The small size ranges of the

    Simmondsia chinensis

    Seed Iron Fluoride removal [33]

    materials possess increased surface area, which helps in the adsorption of pollutants due to increments of active sites. Moreover, the use of plant materials for the green synthesis of nanoparticles is useful for its cost-effectiveness, bulk

    Nettle and

    Thyme Azadirachta indica

    Leaf Iron Cephalexin (CEX)

    antibiotic removal Leaf Iron ammonia nitrogen,

    COD

    [34] [35]

    production, and effective reproducibility process. Table 1.2 represents various plant parts utilized in different literature for synthesizing metal-based nanomaterials.

    Eucalyptus

    teretiornis, Eucalyptus globules

    Leaf Iron Dye removal [36]

    Leaf Iron Chromium [37]

    The production of green nanoparticles provides numerous

    oolong tea Leaf Iron Malachite green [38]

    advantages over traditional methods that include no energy requirement, significant affordability, and eco-friendliness as

    Green tea Iron Methylene blue and methyl orange

    [39]

    no toxic byproducts are produced [35]. The benefit of green produced nanoparticles synthesis is that they do not require

    Lantana

    camara

    Leaf Iron Ni (II) [40]

    synthetic reducing agents, which are detrimental to the environment. Additional benefits of green synthesis over traditional ones include the possibility of bulk scale production, no requirement of external conditions such as high pressure and energy [36].

    Table 1.2. Literature of plant-mediated synthesis of the nanoparticles.

    Oak, mulberry

    and cherry Eichhornia crassipes, Lantana camara and Mimosa pudica

    Leaf Iron Arsenic (III),

    Chromium

    Leaf Iron Nitrate and phosphate

    [41] [42]

    Vaccinium

    Shoot

    Iron Arsenic [43]

    Plant name Plant

    part

    Metal

    salt

    Application Refere

    nces

    corymbosum and leaf
    Benjamina Leaf Silver Cadmium [20] Tea extract Leaf Iron Bromothymol blue [44]
    Trigonella Leaf Silver Reactive blue 19 [21]
    foenum- and Reactive
    graecum yellow 186
    Terminalia Fruit Silver Methyl orange, [22]
    bellerica Eosin yellow
    kernel
    Palm tree Leaf Copper Methylene blue [23]
    (Phoenix silver
    dactylifera)
    Mussaenda Leaf Gold Rhodamine B, [24]
    glabrata and methyl orange

     

    Table 1.2 summarizes the utilization of several plant species for the synthesis of plant-mediated metal nano complexes. Different precursor metal salts like silver, gold, copper, nickel, and iron were used for complexation purposes. Among them, some metal salts are quite costly, which makes the synthesized materials expensive, and some have some toxic effects on the environment. However, the use of iron salt for synthesis makes the material cost-effective and environmentally friendly. Apart from it, iron is a common earth element also very essential for

    the growth of the living body. Iron forms strong bonds with the phenolic OH group of the polyphenols to form a complex. Iron after complexation generally prefers the Fe (III) oxidation state, but in a mixture, some amount of Fe (II) could also be present [60-61].

    Polyphenols can react with iron in various ways depending on pH, iron oxidation state, metal-ligand ratio, and oxygen present. Depending upon pH, polyphenols and polyphenolic- metal complexes can be varied structurally, show different coordination modes [6062]. Iron binds to polyphenol due to the antioxidant actions of polyphenols [64, 71-73].

  2. APPLICATION OF IRON-PLANT POLYPHENOL COMPLEXES IN WASTEWATER TREATMENT
    1. Wastewater Treatment

      Zhu et al. (2018) used green tea extract was utilized for the synthesis of zero-valent iron/Cu nanoparticle synthesis at N2 atmosphere and employed for the removal of Cr (VI) from aqueous solutions [74]. At pH 5, zero-valent iron/Cu nanoparticles were capable of 94.7 % removal of 5 mg/L of Cr

      (VI) solution. The material was characterized y FESEM, FTIR, and PXRD (peak is unclear, polyphenol not measured, no iron-polyphenol ratio). Pan et al. (2019) used peanut skin for iron-based nanoparticles synthesis purposes [75]. This study described the core-shell structure of nano complex with Fe (0) in the core, surrounded by the biomolecule layer. The material was characterized using PXRD, FTIR, XPS, and UV- spectroscopy. Moreover, SEM images showed agglomeration of the particle. Materials showed 100% removal of 10 mg/L of Cr (VI) at pH 4.7 and 2 g/L of dose. Similarly, Jin et al. (2018) synthesized zero-valent iron nanoparticles using eucalyptus leaf extract and applied for chromium removal [76]. The experiment was executed with 10 mg/L of chromium solution, at pH 4, nanoparticle dose of 1.4 g/L, 30C. Results showed 86% removal of total chromium.

      Ehrampoush et al. (2015) utilized tangerine peel extract, which acted as a stabilizing agent for the synthesis of iron oxide nanoparticles by co-precipitation method and utilized for cadmium adsorption [77]. The average size of the particles in DLS was 200 nm. Moreover, the removal experiment showed 88% removal of 20 mg/L of Cd at 4 pH, with a material dose of 4 g/L.

      Machado et al. (2017) utilized the oak leaves to synthesize nanoscale zero-valent iron and analyzed the degradation of a popular antibiotic and amoxicillin in wastewater [78]. They studied the degradation of 100% of amoxicillin occurred at 95 min of contact time in an aqueous solution with amoxicillin and nanoparticle in the ratio of 1:15. Apart from these, Lantana camara fruit extract was used by Nithya et al. (2018) for the synthesis of iron oxide nanoparticles and applied for the removal of Ni (II) [34]. With the dose of the nanoparticle of 1.2 g/L, 99% removal of 100 mg/L of the solution was observed at pH 7. Manquián-Cerda et al. (2017) employed the plant leaves and shoots extract of Vaccinium Corymbosum to synthesize iron nanoparticles and apply them for arsenate removal [58]. Nanoparticles were characterized using TEM, SEM (52 nm), BET, PXRD. They reported that the maximum removal of 76% of 200 mg/L arsenates was observed at pH 4, and 120 min of reaction time. Furthermore, Sajadi et al. (2016) utilized the plant seeds of Silybum marianum L. for the synthesis of copper-supported iron nanoparticles and applied them against

      nitrobenzene reduction [79]. Materials were characterized by XRD, TEM, EDS, and UVvis spectroscopy. Maximum removal of 96% was observed for 1 mmol of concentration at

      90 min of reaction time. The following tables show the summary of plant-mediated iron-nano complexes synthesized by using different plants, characterized, and applied to remove pollutants from wastewater.

      Table 1.3. Use of plant-mediated nanoparticles in wastewater treatment.

      Plant name Application Condition Removal or uptake Comment Refere nces
      Green tea, Nitrate 20 mg/L, 1g dose 50 and 35% Total phenol not measured. EDS only. [45]
      Eucalyptus PXRD peak not clear
      leaf

      Nephrolepis

      Chromium 50 mg/L of 90% XPS, EDS, Fe+3, Fe+2, Fe0 [46]
      auriculata (VI) Nitrogen atmosphere for synthesis. The
      dose is not clear.
      Citrus maxima Chromium 100 mg/L, 90 99% TEM, EDS, XPS, IR, DLS. [47]
      peels (VI) min, Nanoparticles in solution phase. The
      dose of material is not clear. Removal
      was not checked with varying conditions.
      Oak, mulberry and Arsenic (III), 300 mg/g Polyphenol not measured, no [41]
      cherry NPs 200 mg/g and characterization for the state of iron.
      250 mg/g Claim Zero valent NPs
      Tangerine peel Cadmium 4 pH, 4 g/L of 88% No polyphenol estimation. SEM, DLS [48]
      extract dose, 20 mg/L of only. In removal, no triplicates
      Cd
      Nettle and Thyme Cephalexin 25 mg/L, 0.1g 80% Powder XRD, peaks of different state of [34]
      leaf antibiotic dose Fe were there. Claim Zero valent NPs
      Cupressus Methyl 25 mg/L, with 95% Polyphenol not measured. PXRD [49]
      sempervirens leaf

      Hibiscus flower

      orange dye

      Rodamine B

      H2O2, 1 g/L dose 20 mg/g Synthesis and characterization not [50]
      petals cleared, EDS done. Claim Zero valent
      NPs
      Eucalyptus leaf Acid black 71% and 84% [51]
      194 removal Iron-Polyphenol complex
      COD, N
      Oolong tea Malachite 50 mg/L conc, 73% EDS, PXRD. [38]
      green 0.01g dose, in NP in solution phase
      40min.
      Iron-polyphenol Acid red 94 2000 mg/L initial Uptake is 463 IR, TEM only. NPs in solution used. Not [52]
      with Eucalyptus and MB conc. 24hr contact mg/g for acid in powder form. Dose and other
      and 2 other plants time. red and 64 mg/g parameters not clear
      for MB
      Iron-polyphenol Acid black 1300 mg/L of > 80% removal. UV, IR [36]
      with Eucalyptus 194 2000 mg/L initial NPs in solution used. Not in powder
      leaf conc. 24h contact form. Dose and other parameters not
      time. clear
      pH 3-9
      Tea leaf Malachite 0.01 g of dose, 50 Uptake of 190.3 IR, XPS, zeta potential. [19]
      green (MG), mg/L initial conc. mg/g, 186.93/p> Only kinetics study
      methylene mg/g and 182.4
      blue (MB), mg/g, respective
      and
      rhodamine B
      (RB)
      Fe-zero with Guava MB 50 mg/L conc, > 94% removal UV-TEM-IR. [53]
      leaf 2.4g/L dose. Claim Zero valent NPs
      Tea leaf-Iron, Real textile Initial- 350 mg/L 72% removal XRD, SEM, EDX, different modeling. [54]
      NZVI activated water conc. dose 0.7g. for AC, 85% UV peak not mentioned.
      carbon comparison pH 5 for NZVI, 8 removal for
      for AC, and 7 for green nano. And
      green nano. 71% for nZVI
      Fe3O4 coated-tea

      polyphenol

      MB removal 3.5 mg/L conc,

      dose 1g/L, pH >7.

      Uptake 5mg/g ESI mass, PXRD, raman, VSM, BET

      surface area 126

      [55]

      It was observed that no confined protocol was followed for synthesis purposes. In different reports, various kinds of synthesis processes were used. Thus, there exists a scarcity of knowledge regarding detailed analysis of zero-valent iron, irrespective of results reported in various literature. In some literature, the formation of zero-valent iron was claimed without proper characterization of the materials. However, in some literature, iron complexes were separated using centrifugation and applied as a powder form. Whereas, according to some other experimental results, materials were present in the suspension phase. So to say, basically, in all the studies, the efficiency of iron- polyphenol complexes in pollutant removal was studied.

    2. Application in Agriculture

      Iron is an important element for plant growth, photosynthesis capacities, as well as different biochemical processes. It is also crucial for the structure of chloroplasts, as well as Fe-S group is essential to ensure electron flow in the thylakoid membrane [90]. Iron also has an important role in synthesizing chl-b from chl-a [91]. In different literature, iron-based nanomaterials improved plant growth in terms of biomass, root-shoot growth, photosynthesis capacity, productivity, etc. [92,93]. However, some literature reported the negative impact on the plants, like the accumulation of iron nanoparticles in the root surface and cause the suppression of water uptake, suppression on growth, induce stress, etc. [9496]. Table 1.4. Summarizes different studies on the effect of iron-based nanoparticles on plant species.

      Table 1.4. Positive and negative effects of different metal complexes on different plant species.

      Materials Species Analysis Comment Refere nces
      Iron oxide NPs Lemna minor No. of leaves, dry accumulation in chlorophyll, Lipid weight, Fe the root, peroxidation At high concentration, chlorophyll content decrease, MDA production increased. Showed toxicity on plant [56]

      were measured.

      and kill plants within 7 days in all concentration range.

      Iron (III) oxide NPs

      Vigna radiata Dry biomass, root-shoot growth, Fe

      and As analysis, proline test, H2O2 content, total antioxidant capacity, SEM, etc., were measured.

      The effect of Seedlings raised in AsO4 3 and Fe2O3-NPs, and in combined conditions were evaluated in this study. AsO4 3- reduces the seedling growth. Fe2O3-NPs showed resistance to arsenic toxicity.

      [57]

      Micro and nano-sized iron

      Lepidium sativum, Sinapis alba, and Sorghum saccharatum

      Germination index, elongation, biomass, microscopic observation was checked.

      No significant phytotoxicity effects could be detected. Increased seedling length and biomass production were observed.

      [58]

      Fe3O4

      Cucumber and

      Root elongation, germination index,

      Decrease in

      root growth and

      [59]

      nanoparticle

      lettuce

      relative seed germination was checked.

      germination index.

      Zero-valent iron Cattail and

      hybrid poplars plant species

      Root-shoot weight, length were measured. FESEM, EDX, TEM were also checked.

      The result showed the toxic effect on cattail species at >200mg/L of concentration. While at a lower concentration, it enhances plants growth.

      [60]
      FeOx NPs Lactuca sativa Germination test, root shoot length 1mg/L dose helped in germination and growth. However, 20mg/L dose suppressed the germination of seeds. [61]
      Zero-valent iron Oryza sativa cv Germination test, growth, Increased root-shoot length, biomass, [62]
      nanoparticle hydrolytic enzyme activities, and chlorophyll. absence of membrane
      antioxidant, proline, chlorophyll. damage, decrease in proline content.
      Zero-valent iron Peanut Germination test, growth, TEM 40 and 80 mol/L of dose better of [63]
      nanoparticle growth of plants.

      In the above table, it could be seen that iron complexes were able to show positive effects by increasing the plants productivity, growth, and biomass. On the other hand, some literature showed the negative influence of iron complexes on plants, such as the deposition of iron nanoparticles in the root surface, which reduces the water intake, affects growth rate, and induces stress.

    3. Antimicrobial Activity

      The application of iron complexes on nanomaterials has significant potential in the inhibition of various diseases causing bacteria and fungi. Although the mechanism of these metal nano compounds, antimicrobial properties are

      yet to be known. A number of the proposed mechanisms of antimicrobial activities have been suggested, including breakage of the cell membrane, damage of DNA, etc. Lee et al. (2008) studied the effect of zero-valent iron on E. Coli and studied the severe physical disruption of membranes which could have induced oxidative stress and showed the high antimicrobial effects of dissolved iron [104]. However, the absence of a harmful effect of nZVI on the species was observed by Stefaniuk et al. (2016), and further growth of Gram-positive bacteria was found [105]. The following table shows the summary of the inhibition effect of iron polyphenol complexes on different microbes.

      Table 1.5. Antimicrobial activity of iron nanoparticles.

      Materials Species Comments References
      Iron oxide NPs with E. oli and S. epidermidis Kirby-Bauer diffusion assay with 70 µL of material. [64]
      Cynometra ramiflora <p(dose is not clearly mentioned). The exact area of ZOI
      leaf extract is not mentioned.
      Gallic-Aluminium and E. oli Only iron-gallic acid complex is effective in showing [65]
      gallic-iron complex inhibition. ZOI of the iron-gallic complex is 12.00 ±
      0.25 mm with 50L of genotoxic dose.
      Iron oxide NPs with Trichothecium roseum, With 0.5 mg/ml dose of iron nano, the ZOI of the [66]
      tannic acid Cladosporium herbarum, different fungi are as follows:
      Penicillium chrysogenum, T. roseum, (22 mm)
      Alternaria alternata, and C. erbarum, (18 mm)
      Aspergillus niger. P. hrysogenum,(28 mm)
      A. alternate (21 mm) and A. niger (26 mm).
      Iron oxide magnetic E. coli, P. mirabilis and B. 8 mm ZOI with 12.5 µg/disc of dose. [67]
      NPs with Argemone subtilis
      mexicana L. leaf
      extract
      Iron oxide NPs Staphylococcus aureus, With a dose of 0.15 mg/mL of NPs, the ZOI against S. [68]
      Escherichia coli, and aureus, E. coli, and P. aeruginosa is 29,26,28 mm.
      Pseudomonas
      aeruginosa
      Iron oxide NPs Bacillus subtilis and E. coli Showed antimicrobial activity at > 50 µM. relatively at [69]
      high concentrations
      Fe3O4-NPs Bacillus cereus and

      Klebsiella pneumoniae

      With 5 g/mL of MIC, against K. pneumoniae and B. cereus showed [70]
      26 mm and 22 mm zone of inhibitions, respectively.
      MBC for these strains was observed at 40 g/mL of
      Fe3O4-NPs, showing 4050% loss in viable bacterial
      cells and 80 g/mL of concentration exhibiting 9099%
      loss.

      This table summarizes the capabilities of different types of iron nano-complexed against various microorganisms to check their inhibition. Different kinds of methods were used for the estimation of the antimicrobial activity of iron- based materials. The phytochemicals are capable of showing antimicrobial activity and fight against several pathogenic diseases [113]. Literature showed the formation of reactive oxygen species (ROS) that breaks the DNA stand and also causes the death of the cells [111]. The mechanism of inhibition varies from species to species. Considering the small size of the iron complex, it can easily penetrate the bacterial membrane due to the adhesion and deposition of the materials, as a result of which cytolysis occurs [114].

  3. CONCLUSION

    This review consolidates current knowledge on iron plant polyphenol complexes as an emerging category of green nanomaterials with significant environmental relevance. Iron strongly binds with phenolic OH of plants polyphenols. The unique coordination chemistry between iron ions and naturally occurring polyphenols enables the formation of stable, multifunctional nanostructures using environmentally benign synthesis routes. These materials combination of iron with the antioxidant, and antimicrobial properties of polyphenols, resulting in synergistic performance across diverse environmental applications. In wastewater treatment, iron-polyphenol nanomaterials have demonstrated remarkable effectiveness in removing a wide range of contaminants, including heavy metals, synthetic dyes, nutrients, and emerging pollutants. Beyond water remediation, their application in agriculture highlights

  4. REFERENCES
  5. A.S. Adeleye, J.R. Conway, K. Garner, Y. Huang, Y. Su, A.A. Keller, Engineered nanomaterials for water treatment and remediation: Costs, benefits, and applicability, Chem. Eng. J. 286 (2016) 640662. https://doi.org/10.1016/j.cej.2015.10.105.
  6. E.N. Zare, M.M. Lakouraj, N. Kasirian, Development of effective nano-biosorbent based on poly m-phenylenediamine grafted dextrin for removal of Pb (II) and methylene blue from water, Carbohydr. Polym. 201 (2018) 539548. https://doi.org/10.1016/j.carbpol.2018.08.091.
  7. A. Bhatnagar, M. Sillanpää, Utilization of agro-industrial and municipal waste materials as potential adsorbents for water treatment-A review, Chem. Eng. J. 157 (2010) 277296. https://doi.org/10.1016/j.cej.2010.01.007.
  8. M.M. Ayad, A.A. El-nasr, Adsorption of Cationic Dye ( Methylene Blue ) from Water Using Polyaniline Nanotubes Base,

    J. Phys. Chem. 114 (2010) 1437714383.

  9. C. Santhosh, V. Velmurugan, G. Jacob, S.K. Jeong, A.N. Grace,
    1. Bhatnagar, Role of nanomaterials in water treatment applications: A review, Chem. Eng. J. 306 (2016) 11161137. https://doi.org/10.1016/j.cej.2016.08.053.
  10. S. De Gisi, G. Lofrano, M. Grassi, M. Notarnicola, Characteristics and adsorption capacities of low-cost sorbents for wastewater treatment: A review, Sustain. Mater. Technol. 9 (2016) 1040. https://doi.org/10.1016/j.susmat.2016.06.002.
  11. B. Volesky, Biosorbents for metal recovery, Trends Biotechnol. 5 (1987) 96101. https://doi.org/10.1016/0167-7799(87)90027-8.
  12. K. Kaya, E. Pehlivan, C. Schmidt, M. Bahadir, Use of modified wheat bran for the removal of chromium(VI) from aqueous solutions, Food Chem. 158 (2014) 112117. https://doi.org/10.1016/j.foodchem.2014.02.107.
  13. O. Karnitz, L.V.A. Gurgel, J.C.P. de Melo, V.R. Botaro, T.M.S. Melo, R.P. de Freitas Gil, L.F. Gil, Adsorption of heavy metal ion from aqueous single metal solution by chemically modified sugarcane bagasse, Bioresour. Technol. 98 (2007) 12911297. https://doi.org/10.1016/j.biortech.2006.05.013.
  14. L. Bulgariu, L.B. Escudero, O.S. Bello, M. Iqbal, J. Nisar, K.A. Adegoke, F. Alakhras, M. Kornaros, I. Anastopoulos, The utilization of leaf-based adsorbents for dyes removal: A review,

    their role in enhancing iron bioavailability, improving soil

    fertility, and promoting sustainable crop production while

    J. Mol. Liq. 276 (2019)

    https://doi.org/10.1016/j.molliq.2018.12.001.

    728747.

    minimizing environmental risks associated with synthetic agrochemicals. Due to the production of different reactive oxygen species, such as hydroxyl radicals, singlet oxygen, etc., which induce stress and cause resistance against bacteria by damaging the cell. Therefore, the antimicrobial activity of these complexes provides additional value for controlling pathogenic microorganisms in environmental and agricultural systems. Despite these promising attributes, challenges remain related to long-term stability, reusability, mechanistic understanding under complex environmental conditions, and scalability of production. Future reserch should focus on standardizing synthesis protocols, assessing environmental fate and ecotoxicity, and integrating life- cycle and techno-economic assessments. Addressing these gaps will be crucial for translating ironâpolyphenol green nanomaterials from experimental studies to practical, large- scale environmental solutions. Overall, these materials represent a compelling pathway toward sustainable nanotechnology-driven environmental management.

  15. F.M.A.A. Arshad I. Esmael, Minerva E. Matta, Hisham A. Halim, Adsorption of Heavy Metals from Industrial Wastewater using Palm Date Pits as Low Cost Adsorbent, Int. J. Eng. Adv. Technol. 3 (2014) 7176.
  16. L.-H. Wang, C.-I. Lin, Adsorption of Lead(II) Ion from Aqueous Solution Using Rice Hull Ash, Ind. Eng. Chem. Res. 47 (2008) 48914897. https://doi.org/10.1021/ie071521z.
  17. S. Chowdhury, R. Mishra, P. Saha, P. Kushwaha, Adsorption thermodynamics, kinetics and isosteric heat of adsorption of malachite green onto chemically modified rice husk, Desalination. 265 (2011) 159168. https://doi.org/10.1016/j.desal.2010.07.047.
  18. L. Levankumar, V. Muthukumaran, M.B. Gobinath, Batch adsorption and kinetics of chromium (VI) removal from aqueous solutions by Ocimum americanum L. seed pods, J. Hazard. Mater. 161 (2009) 709713.

    https://doi.org/10.1016/j.jhazmat.2008.04.031.

  19. J. Anandkumar, B. Mandal, Removal of Cr(VI) from aqueous solution using Bael fruit (Aegle marmelos correa) shell as an adsorbent, J. Hazard. Mater. 168 (2009) 633640. https://doi.org/10.1016/j.jhazmat.2009.02.136.
  20. A. Al Bsoul, L. Zeatoun, A. Abdelhay, M. Chiha, Adsorption of copper ions from water by different types of natural seed materials, Desalin. Water Treat. 52 (2014) 58765882. https://doi.org/10.1080/19443994.2013.808593.
  21. Z. Zhang, I.M. OHara, G.A. Kent, W.O.S. Doherty,

    Comparative study on adsorption of two cationic dyes by milled

    sugarcane bagasse, Ind. Crops Prod. 42 (2013) 4149. https://doi.org/10.1016/j.indcrop.2012.05.008.

  22. P. Pillai, Y. Lakhtaria, S. Dharaskar, M. Khalid, Synthesis, characterization, and application of iron oxyhydroxide coated with rice husk for fluoride removal from aqueous media, Environ. Sci. Pollut. Res. 27 (2020) 2060620620. https://doi.org/10.1007/s11356-019-05948-8.
  23. K.G. Bhattacharyya, A. Sharma, Adsorption of Pb(II) from aqueous solution by Azadirachta indica (Neem) leaf powder, J. Hazard. Mater. 113 (2004) 97109. https://doi.org/10.1016/j.jhazmat.2004.05.034.
  24. M.A. Ahmad, R. Alrozi, Optimization of rambutan peel based activated carbon preparation conditions for Remazol Brilliant Blue R removal, Chem. Eng. J. 168 (2011) 280285. https://doi.org/10.1016/j.cej.2011.01.005.
  25. R. Han, Y. Wang, X. Zhao, Y. Wang, F. Xie, J. Cheng, M. Tang, Adsorption of methylene blue by phoenix tree leaf powder in a fixed-bed column: experiments and prediction of breakthrough curves, Desalination. 245 (2009) 284297. https://doi.org/10.1016/j.desal.2008.07.013.
  26. T.A. Khan, R. Rahman, E.A. Khan, Decolorization of bismarck brown R and crystal violet in liquid phase using modified pea peels : non-linear isotherm and kinetics modeling, Model. Earth Syst. Environ. 2 (2016) 111. https://doi.org/10.1007/s40808-

    016-0195-6.

  27. K. Johari, N. Saman, S.T. Song, C.S. Chin, H. Kong, H. Mat, Adsorption enhancement of elemental mercury by various surface modified coconut husk as eco-friendly low-cost adsorbents, Int. Biodeterior. Biodegradation. 109 (2016) 4552. https://doi.org/10.1016/j.ibiod.2016.01.004.
  28. Y.C. Sharma, Uma, S.N. Upadhyay, Removal of a cationic dye from wastewaters by adsorption on activated carbon developed from coconut coir, Energy and Fuels. 23 (2009) 29832988. https://doi.org/10.1021/ef9001132.
  29. X. Chen, X. Chen, X. Wan, B. Weng, Q. Huang, Water hyacinth (Eichhornia crassipes) waste as an adsorbent for phosphorus removal from swine wastewater, Bioresour. Technol. 101 (2010) 90259030. https://doi.org/10.1016/j.biortech.2010.07.013.
  30. W. Qu, D. He, Y. Guo, Y. Tang, J. Shang, L. Zhou, R. Zhu, R.J. Song, Modified Water Hyacinth Functionalized with Citric Acid as an Effective and Inexpensive Adsorbent for Heavy Metal-Ion Removal, Ind. Eng. Chem. Res. 58 (2019) 1850818518. https://doi.org/10.1021/acs.iecr.9b03401.
  31. N. Kannan, M.M. Sundaram, Kinetics and mechanism of removal of methylene blue by adsorption on various carbons – A comparative study, Dye. Pigment. 51 (2001) 2540. https://doi.org/10.1016/S0143-7208(01)00056-0.
  32. C. Xiao, H. Li, Y. Zhao, X. Zhang, X. Wang, Green synthesis of iron nanoparticle by tea extract (polyphenols) and its selective removal of cationic dyes, J. Environ. Manage. 275 (2020) 111262. https://doi.org/10.1016/j.jenvman.2020.111262.
  33. V.A. Niraimathee, V. Subha, R.S.E. Ravindran, S. Renganathan, Green synthesis of iron oxide nanoparticles from Mimosa pudica root extract, Int. J. Environ. Sustain. Dev. 15 (2016) 227. https://doi.org/10.1504/IJESD.2016.077370.
  34. S. Venkateswarlu, Y.S. Rao, T. Balaji, B. Prathima, N.V.V. Jyothi, Biogenic synthesis of Fe3O4 magnetic nanoparticles using plantain peel extract, Mater. Lett. 100 (2013) 241244. https://doi.org/10.1016/j.matlet.2013.03.018.
  35. A. Ebrahiminezhad, S. Taghizadeh, Y. Ghasemi, A. Berenjian, Green synthesized nanoclusters of ultra-small zero valent iron nanoparticles as a novel dye removing material, Sci. Total Environ. 621 (2018) 15271532.

    https://doi.org/10.1016/j.scitotenv.2017.10.076.

  36. M.K. Satapathy, P. Banerjee, P. Das, Plant-mediated synthesis of silver-nanocomposite as novel effective azo dye adsorbent, Appl. Nanosci. 5 (2015) 19. https://doi.org/10.1007/s13204-013-0286- x.
  37. K.M. Al-Qahtani, Cadmium removal from aqueous solution by green synthesis zero valent silver nanoparticles with Benjamina leaves extract, Egypt. J. Aquat. Res. 43 (2017) 269274. https://doi.org/10.1016/j.ejar.2017.10.003.
  38. K. Nithya, A. Sathish, P. Senthil Kumar, T. Ramachandran, Fast kinetics and high adsorption capacity of green extract capped superparamagnetic iron oxide nanoparticles for the adsorption of

    Ni(II) ions, J. Ind. Eng. Chem. 59 (2018) 230241.

    https://doi.org/10.1016/j.jiec.2017.10.028.

  39. M. Herlekar, S. Barve, R. Kumar, Plant-Mediated Green Synthesis of Iron Nanoparticles, J. Nanoparticles. 2014 (2014) 1

    9. https://doi.org/10.1155/2014/140614.

  40. M.I. Din, A. Zahoor, Z. Hussain, R. Khalid, A review on green synthesis of iron (Fe) nanomaterials, its alloys and oxides, Inorg. Nano-Metal Chem. 0 (2020) 117. https://doi.org/10.1080/24701556.2020.1862229.
  41. J. Singh, V. Kumar, S. Singh Jolly, K.-H. Kim, M. Rawat, D. Kukkar, Y.F. Tsang, Biogenic synthesis of silver nanoparticles and its photocatalytic applications for removal of organic pollutants in water, J. Ind. Eng. Chem. 80 (2019) 247257. https://doi.org/10.1016/j.jiec.2019.08.002.
  42. L. Sherin, A. Sohail, U.-S. Amjad, M. Mustafa, R. Jabeen, A. Ul- Hamid, Facile green synthesis of silver nanoparticles using Terminalia bellerica kernel extract for catalytic reduction of anthropogenic water pollutants, Colloid Interface Sci. Commun. 37 (2020) 100276. https://doi.org/10.1016/j.colcom.2020.100276.
  43. J. Al-Haddad, F. Alzaabi, P. Pal, K. Rambabu, F. Banat, Green synthesis of bimetallic coppersilver nanoparticles and their application in catalytic and antibacterial activities, Clean Technol. Environ. Policy. 22 (2020) 269277. https://doi.org/10.1007/s10098-019-01765-2.
  44. S. Francis, S. Joseph, E.P. Koshy, B. Mathew, Green synthesis and characterization of gold and silver nanoparticles using Mussaenda glabrata leaf extract and their environmental applications to dye degradation, Environ. Sci. Pollut. Res. 24 (2017) 1734717357. https://doi.org/10.1007/s11356-017-9329-

    2.

  45. B. Bonigala, B. Kasukurthi, V.V. Konduri, U.K. Mangamuri, R. Gorrepati, S. Poda, Green synthesis of silver and gold nanoparticles using Stemona tuberosa Lour and screening for their catalytic activity in the degradation of toxic chemicals, Environ. Sci. Pollut. Res. 25 (2018) 3254032548. https://doi.org/10.1007/s11356-018-3105-9.
  46. B.C. Choudhary, D. Paul, T. Gupta, S.R. Tetgure, V.J. Garole,

    A.U. Borse, D.J. Garole, Photocatalytic reduction of organic pollutant under visible light by green route synthesized gold nanoparticles, J. Environ. Sci. 55 (2017) 236246. https://doi.org/10.1016/j.jes.2016.05.044.

  47. R.M. Paixão, I.M. Reck, R. Bergamasco, M.F. Vieira, A.M.S. Vieira, Activated carbon of Babassu coconut impregnated with copper nanoparticles by green synthesis for the removal of nitrate in aqueous solution, Environ. Technol. (United Kingdom). 39 (2018) 19942003.

    https://doi.org/10.1080/09593330.2017.1345990.

  48. M. Rafique, F. Shafiq, S.S. Ali Gillani, M. Shakil, M.B. Tahir, I. Sadaf, Eco-friendly green and biosynthesis of copper oxide nanoparticles using Citrofortunella microcarpa leaves extract for efficient photocatalytic degradation of Rhodamin B dye form textile wastewater, Optik (Stuttg). 208 (2020) 164053. https://doi.org/10.1016/j.ijleo.2019.164053.
  49. L. Katata-Seru, T. Moremedi, O.S. Aremu, I. Bahadur, Green synthesis of iron nanoparticles using Moringa oleifera extracts and their applications: Removal of nitrate from water and antibacterial activity against Escherichia coli, J. Mol. Liq. 256 (2018) 296304. https://doi.org/10.1016/j.molliq.2017.11.093.
  50. S.C.G. Kiruba Daniel, G. Vinothini, N. Subramanian, K. Nehru,

    M. Sivakumar, Biosynthesis of Cu, ZVI, and Ag nanoparticles using Dodonaea viscosa extract for antibacterial activity against human pathogens, J. Nanoparticle Res. 15 (2013) 1319. https://doi.org/10.1007/s11051-012-1319-1.

  51. M. Jamzad, M. Kamari Bidkorpeh, Green synthesis of iron oxide nanoparticles by the aqueous extract of Laurus nobilis L. leaves and evaluation of the antimicrobial activity, J. Nanostructure Chem. 10 (2020) 193201. https://doi.org/10.1007/s40097-020-

    00341-1.

  52. S. Hossen, M. Yusuf, S. Chandra, T. Das, O. Saha, M. Rahaman,

    J. Islam, Green synthesis of iron oxide nanoparticle using Carica papaya leaf extract : application for photocatalytic degradation of remazol yellow RR dye and antibacterial activity, Heliyon. 6 (2020) e04603. https://doi.org/10.1016/j.heliyon.2020.e04603.

  53. S. Kumari, S. Khan, Defluoridation technology for drinking water and tea by green synthesized Fe3O4/Al2O3 nanoparticles

    coated polyurethane foams for rural communities, Sci. Rep. 7 (2017) 112. https://doi.org/10.1038/s41598-017-08594-7.

  54. M. Leili, M. Fazlzadeh, A. Bhatnagar, Green synthesis of nano- zero-valent iron from Nettle and Thyme leaf extracts and their application for the removal of cephalexin antibiotic from aqueous solutions, 3330 (2018). https://doi.org/10.1080/09593330.2017.1323956.
  55. C.P. Devatha, A.K. Thalla, S.Y. Katte, Green synthesis of iron nanoparticles using different leaf extracts for treatment of domestic waste water, J. Clean. Prod. 139 (2016) 14251435. https://doi.org/10.1016/j.jclepro.2016.09.019.
  56. Z. Wang, Iron complex nanoparticles synthesized by eucalyptus leaves, ACS Sustain. Chem. Eng. 1 (2013) 15511554. https://doi.org/10.1021/sc400174a.
  57. V. Madhavi, T.N.V.K.V. Prasad, A.V.B. Reddy, B. Ravindra Reddy, G. Madhavi, Application of phytogenic zerovalent iron nanoparticles in the adsorption of hexavalent chromium, Spectrochim. Acta – Part A Mol. Biomol. Spectrosc. 116 (2013) 1725. https://doi.org/10.1016/j.saa.2013.06.045.
  58. L. Huang, X. Weng, Z. Chen, M. Megharaj, R. Naidu, Synthesis of iron-based nanoparticles using oolong tea extract for the degradation of malachite green, Spectrochim. Acta – Part A Mol. Biomol. Spectrosc. 117 (2014) 801804. https://doi.org/10.1016/j.saa.2013.09.054.
  59. T. Shahwan, S. Abu Sirriah, M. Nairat, E. Boyac, A.E. Erolu,

    T.B. Scott, K.R. Hallam, Green synthesis of iron nanoparticles and their application as a Fenton-like catalyst for the degradation of aqueous cationic and anionic dyes, Chem. Eng. J. 172 (2011) 258266. https://doi.org/10.1016/J.CEJ.2011.05.103.

  60. S.S. Poguberovi, D.M. Krmar, S.P. Maleti, Z. Kónya, D.D.T. Pilipovi, D. V. Kerkez, S.D. Ronevi, Removal of As(III) and Cr(VI) from aqueous solutions using green zero-valent iron nanoparticles produced by oak, mulberry and cherry leaf extracts, Ecol. Eng. 90 (2016) 4249.

    https://doi.org/10.1016/j.ecoleng.2016.01.083.

  61. R. Prabhakar, S.R. Samadder, Aquatic and terrestrial weed mediated synthesis of iron nanoparticles for possible application in wastewater remediation, J. Clean. Prod. 168 (2017) 1201

    1210. https://doi.org/10.1016/j.jclepro.2017.09.063.

  62. K. Manquián-Cerda, E. Cruces, M. Angélica Rubio, C. Reyes, N. Arancibia-Miranda, Preparation of nanoscale iron (oxide, oxyhydroxides and zero-valent) particles derived from blueberries: Reactivity, characterization and removal mechanism of arsenate, Ecotoxicol. Environ. Saf. 145 (2017) 6977. https://doi.org/10.1016/j.ecoenv.2017.07.004.
  63. H. Xin, X. Yang, X. Liu, X. Tang, L. Weng, Y. Han, Biosynthesis of Iron Nanoparticles Using Tie Guanyin Tea Extract for Degradation of Bromothymol Blue, J. Nanotechnol. 2016 (2016). https://doi.org/10.1155/2016/4059591.
  64. J. Bijlsma, W.J.C. de Bruijn, J.A. Hageman, P. Goos, K.P. Velikov, J.P. Vincken, Revealing the main factors and two-way interactions contributing to food discolouration caused by iron- catechol complexation, Sci. Rep. 10 (2020). https://doi.org/10.1038/s41598-020-65171-1.
  65. M.J. Sever, J.J. Wilker, Visible absorption spectra of metal

    catecholate and metal tironate, (2004) 10611072.

  66. M. Elhabiri, C. Carrër, F. Marmolle, H. Traboulsi, Complexation of iron(III) by catecholate-type polyphenols, Inorganica Chim. Acta. 360 (2007) 353359.

    https://doi.org/10.1016/j.ica.2006.07.110.

  67. R.C. Hider, Z.D. Liu, H.H. Khodr, Metal chelation of polyphenols, in: 2001: pp. 190203. https://doi.org/10.1016/S0076-6879(01)35243-6.
  68. N.R. Perron, J.L. Brumaghim, A review of the antioxidant mechanisms of polyphenol compounds related to iron binding, Cell Biochem. Biophys. 53 (2009) 75100. https://doi.org/10.1007/s12013-009-9043-x.
  69. L.D. Loomis, K.N. Raymond, Solution Equilibria of Enterobactin and Metal-Enterobactin Complexes, Inorg. Chem. 30 (1991) 906911. https://doi.org/10.1021/ic00005a008.
  70. K. Chvátalová, I. Slaninová, L. Bezinová, J. Slanina, Influence of dietary phenolic acids on redoxstatus of iron: Ferrous iron autoxidation and ferric iron reduction, Food Chem. 106 (2008) 650660. https://doi.org/10.1016/j.foodchem.2007.06.028.
  71. H. El Hajji, E. Nkhili, V. Tomao, O. Dangles, Interactions of

    quercetin with iron and copper ions: Complexation and autoxidation, Free Radic. Res. 40 (2006) 303320. https://doi.org/10.1080/10715760500484351.

  72. T. Kawabata, V. Schepkin, N. Haramaki, R.S. Phadke, L. Packer, Iron coordination by catechol derivative antioxidants, Biochem. Pharmacol. 51 (1996) 15691577. https://doi.org/10.1016/0006-

    2952(96)00101-3.

  73. R.K. Feller, A.K. Cheetham, Fe(III), Mn(II), Co(II), and Ni(II) 3,4,5-trihydroxybenzoate (gallate) dihydrates; a new family of hybrid framework materials, Solid State Sci. 8 (2006) 1121

    1125. https://doi.org/10.1016/j.solidstatesciences.2006.04.013.

  74. C. H Wunderlich, R. Weber, G. Bergerhoff, Über Eisengallustinte, ZAAC J. Inorg. Gen. Chem. 598 (1991) 371

    376. https://doi.org/10.1002/zaac.19915980134.

  75. A. Ponce, L.B. Brostoff, S.K. Gibbons, P. Zavalij, C. Viragh, J. Hooper, S. Alnemrat, K.J. Gaskell, B. Eichhorn, Elucidation of the Fe(III) Gallate Structure in Historical Iron Gall Ink, Anal. Chem. 88 (2016) 51525158.

    https://doi.org/10.1021/acs.analchem.6b00088.

  76. C. Krekel, Chemistry of Historical Iron Gall Inks, Int. J. Forensic Doc. Exam. 5 (1999) 548.

    https://www.ncjrs.gov/App/abstractdb/AbstractDBDetails.aspx?i d=186065.

  77. R.F.V. De Souza, E.M. Sussuchi, W.F. De Giovani, Synthesis, electrochemical, spectral, and antioxidant properties of complexes of flavonoids with metal ions, Synth. React. Inorg. Met. Chem. 33 (2003) 11251144. https://doi.org/10.1081/SIM-

    120023482.

  78. F. Zhu, S. Ma, T. Liu, X. Deng, Green synthesis of nano zero- valent iron/Cu by green tea to remove hexavalent chromium from groundwater, J. Clean. Prod. 174 (2018) 184190. https://doi.org/10.1016/j.jclepro.2017.10.302.
  79. Z. Pan, Y. Lin, B. Sarkar, G. Owens, Z. Chen, Green synthesis of iron nanoparticles using red peanut skin extract: Synthesis mechanism, characterization and effect of conditions on chromium removal, J. Colloid Interface Sci. 558 (2019) 106114. https://doi.org/10.1016/j.jcis.2019.09.106.
  80. X. Jin, Y. Liu, J. Tan, G. Owens, Z. Chen, Removal of Cr(VI) from aqueous solutions via reduction and absorption by green synthesized iron nanoparticles, J. Clean. Prod. 176 (2018) 929

    936. https://doi.org/10.1016/j.jclepro.2017.12.026.

  81. M.H. Ehrampoush, M. Miria, M.H. Salmani, A.H. Mahvi, Cadmium removal from aqueous solution by green synthesis iron oxide nanoparticles with tangerine peel extract, J. Environ. Heal. Sci. Eng. 13 (2015) 17. https://doi.org/10.1186/s40201-015-

    0237-4.

  82. S. Machado, J.G. Pacheco, H.P.A. Nouws, J.T. Albergaria, C. Delerue-Matos, Green zero-valent iron nanoparticles for the degradation of amoxicillin, Int. J. Environ. Sci. Technol. 14 (2017) 11091118. https://doi.org/10.1007/s13762-016-1197-7.
  83. S.H. Ali, T.E. Jassim, Thermodynamics and Kinetic study of Bismarck Brown R Dye Adsorption from Aqueous Solution using Sewage Sludge, xxx (2020).
  84. T. Wang, J. Lin, Z. Chen, M. Megharaj, R. Naidu, Green synthesized iron nanoparticles by green tea and eucalyptus leaves extracts used for removal of nitrate in aqueous solution, J. Clean. Prod. 83 (2014) 413419.

    https://doi.org/10.1016/J.JCLEPRO.2014.07.006.

  85. Y. Yi, G. Tu, P. Eric, S. Xiao, Z. Fang, Green synthesis of iron- based nanoparticles from extracts of Nephrolepis auriculata and applications for Cr ( VI ) removal, Mater. Lett. 234 (2019) 388

    391. https://doi.org/10.1016/j.matlet.2018.09.137.

  86. Y. Wei, Z. Fang, L. Zheng, L. Tan, E.P. Tsang, Green synthesis of Fe nanoparticles using Citrus maxima peels aqueous extracts, Mater. Lett. 185 (2016) 384386.

    https://doi.org/10.1016/j.matlet.2016.09.029.

  87. Z. Khan, S.A. Al-Thabaiti, Green synthesis of zero-valent Fe- nanoparticles: Catalytic degradation of rhodamine B, interactions with bovine serum albumin and their enhanced antimicrobial activities, J. Photochem. Photobiol. B Biol. 180 (2018) 259267. https://doi.org/10.1016/j.jphotobiol.2018.02.017.
  88. Z. Wang, C. Fang, M. Megharaj, Characterization of iron- polyphenol nanoparticles synthesized by three plant extracts and their fenton oxidation of azo dye, ACS Sustain. Chem. Eng. 2 (2014) 10221025. https://doi.org/10.1021/sc500021n.
  89. L. Huang, X. Weng, Z. Chen, M. Megharaj, R. Naidu, Synthesis of iron-based nanoparticles using oolong tea extract for the degradation of malachite green, Spectrochim. Acta – Part A Mol. Biomol. Spectrosc. 117 (2014) 801804. https://doi.org/10.1016/j.saa.2013.09.054.
  90. Z. Wang, C. Yu, C. Fang, M. Megharaj, Removal of acid red 94 and methylene blue using iron-polyphenol nanomaterials synthesized by various plant leaves: A comparison study, Proc. 2014 Int. Conf. Nanosci. Nanotechnology, ICONN 2014. (2014)

    3942. https://doi.org/10.1109/ICONN.2014.6965256.

  91. P. Somchaidee, K. Tedsree, Green synthesis of high dispersion and narrow size distribution of zero-valent iron nanoparticles using guava leaf (Psidium guajava L) extract, Adv. Nat. Sci. Nanosci. Nanotechnol. 9 (2018). https://doi.org/10.1088/2043- 6254/aad5d7.
  92. A. Karam, K. Zaher, A.S. Mahmoud, Comparative Studies of Using Nano Zerovalent Iron, Activated Carbon, and Green Synthesized Nano Zerovalent Iron for Textile Wastewater Color Removal Using Artificial Intelligence, Regression Analysis, Adsorption Isotherm, and Kinetic Studies, Air, Soil Water Res. 13 (2020). https://doi.org/10.1177/1178622120908273.
  93. K.K. Singh, K.K. Senapati, K.C. Sarma, Synthesis of superparamagnetic Fe3O4 nanoparticles coated with green tea polyphenols and their use for removal of dye pollutant from aqueous solution, J. Environ. Chem. Eng. 5 (2017) 22142221. https://doi.org/10.1016/j.jece.2017.04.022.
  94. J.F. Briat, C. Dubos, F. Gaymard, Iron nutrition, biomass production, and plant product quality, Trends Plant Sci. 20 (2015) 3340. https://doi.org/10.1016/j.tplants.2014.07.005.
  95. A. Tanaka, R. Tanaka, Chlorophyll metabolism, Curr. Opin. Plant Biol. 9 (2006) 248255.

    https://doi.org/10.1016/j.pbi.2006.03.011.

  96. G. Libralato, A. Costa Devoti, M. Zanella, E. Sabbioni, I. Mieti, L. Manodori, A. Pigozzo, S. Manenti, F. Groppi, A. Volpi Ghirardini, Phytotoxicity of ionic, micro- and nano-sized iron in three plant species, Ecotoxicol. Environ. Saf. 123 (2016) 8188. https://doi.org/10.1016/j.ecoenv.2015.07.024.
  97. J. Trujillo-Reyes, S. Majumdar, C.E. Botez, J.R. Peralta-Videa,

    J.L. Gardea-Torresdey, Exposure studies of core-shell Fe/Fe3O4 and Cu/CuO NPs to lettuce (Lactuca sativa) plants: Are they a potential physiological and nutritional hazard?, J. Hazard. Mater.

    267 (2014) 255263.

    https://doi.org/10.1016/j.jhazmat.2013.11.067.

  98. X. Ma, A. Gurung, Y. Deng, Phytotoxicity and uptake of nanoscale zero-valent iron (nZVI) by two plant species, Sci. Total Environ. 443 (2013) 844849. https://doi.org/10.1016/j.scitotenv.2012.11.073.
  99. D. Martínez-Fernández, D. Barroso, M. Komárek, Root water transport of Helianthus annuus L. under iron oxide nnoparticle exposure, Environ. Sci. Pollut. Res. 23 (2016) 17321741. https://doi.org/10.1007/s11356-015-5423-5.
  100. C.O. Dimkpa, J.E. McLean, N. Martineau, D.W. Britt, R. Haverkamp, A.J. Anderson, Silver nanoparticles disrupt wheat (Triticum aestivum L.) growth in a sand matrix, Environ. Sci. Technol. 47 (2013) 10821090.

    https://doi.org/10.1021/es302973y.

  101. L.R.R. Souza, L.E. Bernardes, M.F.S. Barbetta, M.A.M.S. da Veiga, Iron oxide nanoparticle phytotoxicity to the aquatic plant Lemna minor: effect on reactive oxygen species (ROS) production and chlorophyll a/chlorophyll b ratio, Environ. Sci. Pollut. Res. 26 (2019) 2412124131.

    https://doi.org/10.1007/s11356-019-05713-x.

  102. N. Shabnam, M. Kim, H. Kim, Ecotoxicology and Environmental Safety Iron ( III ) oxide nanoparticles alleviate arsenic induced stunting in Vigna radiata, Ecotoxicol. Environ. Saf. 183 (2019) 109496. https://doi.org/10.1016/j.ecoenv.2019.109496.
  103. R. Barrena, E. Casals, J. Colón, X. Font, A. Sánchez, V. Puntes, Evaluation of the ecotoxicity of model nanoparticles, Chemosphere. 75 (2009) 850857. https://doi.org/10.1016/j.chemosphere.2009.01.078.
  104. X. Ma, A. Gurung, Y. Deng, Phytotoxicity and uptake of nanoscale zero-valent iron (nZVI) by two plant species, Sci. Total Environ. 443 (2013) 844849. https://doi.org/https://doi.org/10.1016/j.scitotenv.2012.11.073.
  105. R. Liu, H. Zhang, R. Lal, Effects of Stabilized Nanoparticles of

    Copper, Zinc, Manganese, and Iron Oxides in Low Concentrations on Lettuce (Lactuca sativa) Seed Germination: Nanotoxicants or Nanonutrients?, Water, Air, Soil Pollut. 227 (2016) 42. https://doi.org/10.1007/s11270-015-2738-2.

  106. T. Guha, K.V.G. Ravikumar, A. Mukherjee, A. Mukherjee, R. Kundu, Nanopriming with zero valent iron (nZVI) enhances germination and growth in aromatic rice cultivar (Oryza sativa cv. Gobindabhog L.), Plant Physiol. Biochem. 127 (2018) 403

    413. https://doi.org/10.1016/j.plaphy.2018.04.014.

  107. X. Li, Y. Yang, B. Gao, M. Zhang, Stimulation of peanut seedling development and growth by zero-valent iron nanoparticles at low concentrations, PLoS One. 10 (2015). https://doi.org/10.1371/journal.pone.0122884.
  108. C. Lee, J.E.E.Y. Kim, W.O.N.I.L. Lee, K.L. Nelson, Bactericidal Effect of Zero-Valent Iron Nanoparticles on Escherichia coli, (2008) 49274933. https://doi.org/10.1021/es800408u.
  109. M. Stefaniuk, P. Oleszczuk, Y.S. Ok, Review on nano zerovalent iron (nZVI): From synthesis to environmental applications, Chem. Eng. J. 287 (2016) 618632.

    https://doi.org/10.1016/j.cej.2015.11.046.

  110. S. Groiss, R. Selvaraj, T. Varadavenkatesan, R. Vinayagam, Structural characterization, antibacterial and catalytic effect of iron oxide nanoparticles synthesised using the leaf extract of Cynometra ramiflora, J. Mol. Struct. 1128 (2017) 572578. https://doi.org/10.1016/j.molstruc.2016.09.031.
  111. J.M. Barcelo, M. Guieb, A. Ventura, A. Nacino, H. Pinasen, L. Viernes, T. Yodong, B. Lou Estrada, D. Valdez, T. Binwag, Antibacterial, Prooxidative and Genotoxic Activities of Gallic Acid and its Copper and Iron Complexes against Escherichia coli, Asia Pacific J. Multidiscip. Res. P. 2 (2014) 23507756. www.apjmr.com.
  112. S. Parveen, A.H. Wani, M.A. Shah, H.S. Devi, M.Y. Bhat, J.A. Koka, Preparation, characterization and antifungal activity of iron oxide nanoparticles, Microb. Pathog. 115 (2018) 287292. https://doi.org/https://doi.org/10.1016/j.micpath.2017.12.068.
  113. S. Arokiyaraj, M. Saravanan, N.K. Udaya Prakash, M. Valan Arasu, B. Vijayakumar, S. Vincent, Enhanced antibacterial activity of iron oxide magnetic nanoparticles treated with Argemone mexicana L. leaf extract: An in vitro study, Mater. Res. Bull. 48 (2013) 33233327.

    https://doi.org/https://doi.org/10.1016/j.materresbull.2013.05.059

  114.  

    M. Thukkaram, S. Sitaram, S. kumar Kannaiyan, G. Subbiahdoss, Antibacterial Efficacy of Iron-Oxide Nanoparticles against Biofilms on Different Biomaterial Surfaces, Int. J. Biomater. 2014 (2014) 716080.

    https://doi.org/10.1155/2014/716080.

  115. M. Arakha, S. Pal, D. Samantarrai, T.K. Panigrahi, B.C. Mallick,

    K. Pramanik, B. Mallick, S. Jha, Antimicrobial activity of iron oxide nanoparticle upon modulation of nanoparticle-bacteria interface, Sci. Rep. 5 (2015) 112. https://doi.org/10.1038/srep14813.

  116. S.A. Ansari, M. Oves, R. Satar, A. Khan, S.I. Ahmad, M.A. Jafri,

    S.K. Zaidi, M.H. Alqahtani, Antibacterial activity of iron oxide nanoparticles synthesized by co-precipitation technology against Bacillus cereus and Klebsiella pneumoniae, Polish J. Chem. Technol. 19 (2017) 110115. https://doi.org/10.1515/pjct-2017-

    0076.

  117. K.B. Myint, L.C. Sing, Z. Wei, Tannic Acid as Phytochemical Potentiator for Antibiotic Resistance Adaptation, APCBEE Procedia. 7 (2013) 175181.

    https://doi.org/10.1016/j.apcbee.2013.08.030.

  118. Y. Vitta, M. Figueroa, M. Calderon, C. Ciangherotti, Synthesis of iron nanoparticles from aqueous extract of Eucalyptus robusta Sm and evaluation of antioxidant and antimicrobial activity, Mater. Sci. Energy Technol. 3 (2020) 97103. https://doi.org/10.1016/j.mset.2019.10.014.