Diversity of Mycogenic Oxide and Chalcogenide Nanoparticles: History
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Contributor:
Ekaterina A. Loshchinina
,
Elena P. Vetchinkina
,
Maria A. Kupryashina

Oxide and chalcogenide nanoparticles have great potential for use in biomedicine, engineering, agriculture, environmental protection, and other research fields. The myco-synthesis of nanoparticles with fungal cultures, their metabolites, culture liquids, and mycelial and fruit body extracts is simple, cheap and environmentally friendly. The characteristics of nanoparticles, including their size, shape, homogeneity, stability, physical properties and biological activity, can be tuned by changing the myco-synthesis conditions.

  • biogenic nanoparticles
  • green synthesis
  • oxides
  • chalcogenides
  • nanoparticle characteristics

1. Introduction

Nanotechnology and nanomaterials science are rapidly developing fields, which contribute greatly to the development of modern technology and biomedicine. An important challenge is the development of simple, effective, and cheap methods of producing highly monodispersed, stable, and biocompatible nanoparticles (NPs) with the required chemical composition, shape, size, biological activity, and other properties. The recent increase in attention to environmental safety, natural resource exhaustibility, and human health safety has led to the increasing development of green NP-producing technologies by biosynthesis methods [1][2][3][4]. Owing to its being environmentally benign and less resource-intensive than other methods, the synthesis of nontoxic and biocompatible NPs by using living organisms and a variety of biological materials derived from them is a promising alternative to physical and chemical fabrication methods.
The ability to biosynthesize NPs has been found in many organisms, including animals, plants, bacteria, fungi, actinomycetes, algae, lichens, and viruses [5]. Among this diversity of biological objects used for green NP synthesis, a special place is occupied by fungi [6][7][8]. Fungal cultures produce a wide range of proteins with high enzymatic activity, and due to that they can convert metals and other elements into less toxic forms. This includes the formation of NPs, which then accumulate in large quantities within the mycelium and/or extracellularly. As a result, micro- and macro-mycetes from different taxonomic groups can be successfully used to produce NPs and nanomaterials on an industrial scale. The applications of fungi in myco-nano-synthesis are also highly versatile. NPs with different characteristics can be obtained either by growing fungal cultures on media with precursors or by incubating these precursors with mycelial bio-mass, culture liquid filtrates, extracts from vegetative mycelium, fruiting bodies and other morpho-structures, and purified proteins and other metabolites isolated from fungi [5]. In addition, the properties of biogenic NPs depend on medium composition, chemical composition and concentration of the precursor, incubation time, stirring rate, temperature, pH and other conditions. By varying these, the chemical composition, shape, size, homogeneity, stability, and biological activity of formed particles can be controlled [9][10][11][12].

2. Myco-Synthesis of Oxide Nanoparticles

To date, the ability to form elementary metal and metalloid NPs has been found in many fungal species. However, the number of elements that can be sources of mycogenic NPs is rather small and includes gold, silver, platinum, palladium, iron, copper, selenium, and tellurium [5]. For oxides and salts, the range of chemical composition for mycogenic NPs is much wider, yet most of them remain very poorly studied. Among fungi-mediated oxide NPs, titanium, zinc, iron, and copper oxides have been studied to the greatest extent.

2.1. Myco-Synthesis of Copper Oxide Nanoparticles

Copper oxide NPs have attracted high attention because copper is one of the most important elements in modern technologies and is readily accessible [13]. Copper oxide is widely used in catalysis, superconductors, thermoelectric and sensing materials, ceramics, gas sensors, and many other fields. Biomedical applications of these NPs include biosensors, cancer medicine, and antimicrobials [14]. In recent years, the fungi-mediated synthesis of copper oxide NPs has become of interest (Table 1).
Table 1. Myco-synthesis of copper oxide nanoparticles.
NP Species Source Precursors Shape and Size Reference
CuO Aspergillus flavus Culture liquid CuSO4 Spherical (average size of 32.4 nm) [15]
CuO Aspergillus terreus Culture liquid CuSO4 – [16][17]
CuO Aspergillus terreus Culture liquid CuSO4 Below 100 nm [18]
CuO Penicillium chrysogenum Culture liquid CuSO4 Spherical (average size of 9.7 nm) [19]
CuO Trichoderma asperellum Mycelial extract Cu(NO3)2 Spherical (10–190 nm) [20]
CuO Trichoderma harzianum Mycelial extract CuSO4 Nano-fibers (38–77 nm in width, 135–320 nm in length) [21]
Cu2O, CuO Stereum hirsutum Mycelial extract CuCl2 Spherical (5–20 nm) [22]
CuxOy Penicillium aurantiogriseum Culture liquid CuSO4 Spherical (89–250 nm) [23]
CuxOy Penicillium citrinum Culture liquid CuSO4 Spherical (85–295 nm) [23]
CuxOy Penicillium waksmanii Culture liquid CuSO4 Spherical (79–179 nm) [23]
CuxOy Pleurotus florida Bio-mass CuCl2 Spherical, partially spherical, oval (22.55–60.09 nm) [24]
CuSO4 Hexagonal, partially spherical (12.82–48.86 nm)
CuO nanospheres (average size 32.4 nm) with high antimicrobial and antitumor activities were obtained with Aspergillus flavus culture liquid [15]. CuO NPs synthesized with Aspergillus terreus culture liquid showed anticancer activity in a concentration-dependent manner [18]. Other works showed that CuO nanospheres synthesized with A. terreus culture liquid had potent antioxidant and antimicrobial activities [16][17].

2.2. Myco-Synthesis of Iron Oxide Nanoparticles

Iron oxide is a mineral compound that exists in various polymorphic forms, the main of which are hematite (α-Fe2O3), maghemite (γ-Fe2O3), and magnetite (Fe3O4) [25]. Mycogenic NPs of iron oxides (III) and (IV) obtained by different researchers with different biological objects and precursors differ greatly in both size and shape (Table 2). Spherical, cubic, irregular, octahedral, and flakelike iron oxide nanoparticles were obtained with mushroom cultures.
Table 2. Myco-synthesis of iron oxide nanoparticles.
NP Species Source Precursors Shape and Size Reference
α-Fe2O3 Trichoderma harzianum Mycelial extract FeCl3 Spherical (average size of 207 nm) [26]
γ-Fe2O3 Penicillium expansum Mycelial extract FeCl3 Spherical (15.0–66.0 nm) [27]
γ-Fe2O3/α-Fe2O3 Alternaria alternata Mycelial extract Fe(NO3)3 Cubic (average size of 9 nm) [28]
Fe2O3 Aspergillus niger Bio-mass FeCl3 – [29]
Fe2O3 Fusarium incarnatum Culture liquid FeCl2 + FeCl3 Spherical (average size of 30.56 nm) [30]
Fe2O3 Phialemoniopsis ocularis Culture liquid FeCl2 + FeCl3 Spherical (average size of 13.13 nm) [30]
Fe2O3 Penicillium pimiteouiense Culture liquid FeCl2 + FeCl3 Spherical (2–16 nm) [31]
Fe2O3 Trichoderma asperellum Culture liquid FeCl2 + FeCl3 Spherical (average size of 25 nm) [30]
Fe3O4 Aspergillus niger Mycelial extract FeCl3 Nanoflakes (20–40 nm) [32]
Fe3O4 Aspergillus terreus Culture liquid Fe(NO3)3 Spherical [16][17]
Fe3O4 Aspergillus tamarii Culture liquid FeSO4 + FeCl3 Spherical (5–22 nm) [33]
Fe3O4 Fusarium oxysporum Bio-mass K3[Fe(CN)6] + K4[Fe(CN)6] Quasi-spherical (20–50 nm) [34]
Fe3O4 Fusarium solani Bio-mass Fe2O3 Cubic, spherical, irregular (55.3–84.2 nm) [35]
Fe3O4 Verticillium sp. Bio-mass K3[Fe(CN)6] + K4[Fe(CN)6] Cubo-octahedral (100–400 nm) [34]
FexOy Amanita muscaria Fruit body extract FeCl2 + FeCl3 2.2–2.5 nm [36]
FexOy Aspergillus japonicus Bio-mass K3[Fe(CN)6] + K4[Fe(CN)6] Cubic (60–70 nm) [37]
FexOy Pleurotus florida Bio-mass FeCl2 Cubic (11.90–167.63 nm) [24]
FeSO4 Spherical (11.16–98.81 nm), highly agglomerated

2.3. Titanium Oxide NPs

Titanium oxide (TiO2) NPs are yet another important NPs with outstanding properties. Three mineral forms of TiO2 that are known to occur naturally are anatase, rutile, and brookite. TiO2 NPs have a wide range of applications owing to their chemical stability, low toxicity, biocompatibility, and good corrosion resistance [38]. Thanks to their high antibacterial, antifungal, antiviral, and anticancer activity, they are important tools in diagnostics, therapeutics, and drug delivery [39]. Various micro- and macro-mycetes can produce TiO2 NPs with their living cultures, extracts, bio-mass, and even spores (Table 3).
Table 3. Myco-synthesis of titanium oxide nanoparticles.
NP Species Source Precursors Shape and Size Reference
TiO2 Agaricus bisporus Spores Ti(OC3H7)4 – [40]
TiO2 Aspergillus flavus Bio-mass TiO2 Spherical, oval (62–74 nm) [41]
TiO2 Aspergillus flavus Mycelial extract TiO2 12–15 nm [42]
TiO2 Aspergillus niger Mycelial extract TiO2 salt Spherical (73.58–106.9 nm) [43]
TiO2 Aspergillus tubingensis Mycelial extract TiO2 salt Cubic, pentangular (1.5–30 nm) [44]
TiO2 Fomes fomentarius Fruit body extract Ti{OCH(CH3)2}4 Irregular (80–120 nm) [45]
TiO2 Fomitopsis pinicola Fruit body extract Ti{OCH(CH3)2}4 Irregular (80–120 nm) [46]
TiO Fusarium oxysporum Bio-mass K2TiF6 Spherical (6–13 nm) [47]
TiO2 Humicola sp. Bio-mass Bulk TiO2 Spherical (5–28 nm) [48]
TiO2 Hypsizygus ulmarius Fruit body extract TiCl4 Spherical (average size of 80 nm) [49]
TiO2 Pleurotus djamor Fruit body extract TiCl4 Spherical (average size of 31 nm) [50]
TiO2 Pleurotus sajor caju Fruit body extract TiCl4 Spherical (average size of 85 nm) [51]
TiO2 Sachharomyces cerevisae Living culture TiO(OH)2 Spherical (average size of 12.57 nm) [52]
TiO2 Sachharomyces cerevisae Living culture TiCl4 Oval (10–12 nm), mesoporous [53]
TiO2 Sachharomyces cerevisae Living culture TiCl3 Spherical (average size of 6.7 nm) [54]
TiO2 Tricoderma citrinoviride Mycelial extract Ti{OCH(CH3)2}4 Irregular, triangular, pentagonal, spherical, rod-shaped (10–400 nm) [55]
TiO2 Trichoderma viride Culture liquid TiO(OH)2 Spherical (60–86.67 nm) [56]
The ability to synthesize TiO2 NPs was found in various Aspergillus species. Spherical and oval 62–74-nm TiO2 NPs with antibacterial properties were fabricated with A. flavus bio-mass [41]. TiO2 NPs of 12–15 nm synthesized with an A. flavus mycelial extract demonstrated a strong growth-enhancing effect on mung beans and thus can be used as a plant nutrient fertilizer [42]. TiO2 nanospheres (73.58–106.9 nm) generated with an A. niger extract were found a potent mosquito larvicidal agent [43]. TiO2 NPs produced with an Aspergillus tubingensis mycelial extract were cubic and pentameric, with a size of 1.5–30 nm [44].

2.4. Myco-Synthesis of Zinc Oxide Nanoparticles

Zinc oxide (ZnO) NPs have caught the attention of researchers owing to their extensive biological properties, including antibacterial, antifungal, anticancer, anti-inflammatory, antidiabetic, antioxidant, antiviral, wound healing, and cardioprotective activity [57][58]. Their exceptional optical, electrical, and physiochemical properties make ZnO NPs an excellent option for electronics, optoelectronics, bioimaging, biosensors, drug and gene delivery [58][59]. To date, these NPs have been the most commonly studied of all mycogenic oxide NPs (Table 4). Mycogenic ZnO NPs are mostly spherical or hexagonal.
Table 4. Myco-synthesis of zinc oxide nanoparticles.
NP Species Source Precursors Shape and Size Reference
ZnO Acremonium potronii Mycelial extract Zn(CH3CO2)2 Spherical (13–15 nm) [60]
ZnO Agarius bisporus Fruit body extract Zn(CH3CO2)2 Spherical (average size of 14.48 nm) [61]
ZnO Aspergillus aeneus Mycelial extract Zn(CH3CO2)2 Spherical (100–140 nm) [62]
ZnO Aspergillus fumigatus Culture liquid ZnSO4 Spherical (60–80 nm) [63]
ZnO Aspergillus fumigatus Mycelial extract Zn(NO3)2 Oblate spherical and hexagonal (1.2–6.8 nm) [64]
ZnO Aspergillus niger Mycelial extract Zn(CH3CO2)2 Nanorods (8–38 nm) [65]
ZnO Aspergillus niger Crushed fungal powder ZnCl2 Hexagonal (average size of 66 nm) [66]
ZnO Aspergillus terreus Culture liquid ZnSO4 Spherical (28–63 nm) [67]
ZnO Aspergillus terreus Mycelial extract Zn(CH3CO2)2 Spherical (10–45 nm) [68]
ZnO Aspergillus terreus Culture liquid ZnC4H6O4 Almost spherical [16][17]
ZnO Cochliobolus geniculatus Mycelial extract Zn(CH3CO2)2 Quasi-spherical (2–6 nm) [69]
ZnO Cordyceps militaris Fruit body extract Zn(CH3CO2)2 Spherical, irregular (average size of 1.83 nm) [70]
ZnO Daedalea sp. Fruit body extract Zn(CH3CO2)2 Irregular (average size of 14.58 nm) [71]
ZnO Fusarium keratoplasticum Mycelial extract Zn(CH3CO2)2 Hexagonal (10–42 nm) [65]
ZnO Lentinula edodes Fruit body extract Zn(NO3)2 Cubic, hexagonal (average size of 50 nm) [72]
ZnO Periconium sp. Mycelial extract Zn(NO3)2 Quasi-spherical (16–78 nm) [73]
ZnO Pichia kudriavzevii Fungal extract Zn(CH3CO2)2 Hexagonal (average size of 32 nm) [74]
ZnO Pleurotus djamor Fruit body extract Zn(NO3)2 Nanorods, clusters (average size of 70–80 nm) [50]
ZnO Pleurotus florida Bio-mass ZnCl2 Semi-spherical (21.27–118.36 nm) [24]
ZnSO4 Semi-spherical (9.36–58.13 nm)
ZnO Pleurotus floridanus Culture liquid Zn(NO3)2 Spherical (average size of 34.98 nm) [75]
ZnO Pleurotus ostreatus Fruit body extract Zn(NO3)2 Spherical (average size of 7.50 nm) [76]
ZnO Trichoderma harzianum Mycelial extract ZnSO4 Fan- and bouquet-like structures (27–40 nm in width, 134–200 nm in length) [21]
ZnO Trichoderma harzianum Mycelial extract Zn(CH3CO2)2 Spherical (average size of 30.34 nm) [77]
ZnO Trichoderma viride Culture liquid Zn(CH3CO2)2 Hexagonal (average size of 63.3 nm) [78]
The formation of ZnO nanospheres with sizes ranging between 13 and 15 nm was studied by using an Acremonium potronii mycelial extract [60]. The obtained ZnO NPs showed high photocatalytic activity for the degradation of methylene blue dye. ZnO nanospheres with an average size of 14.48 nm were fabricated with an aqueous extract of Agarius bisporus as a reducing agent [61]. These NPs were effective inhibitors of microbially influenced corrosion.
The correlation between the zinc tolerance of soil fungi and their potential for the synthesis of ZnO NPs was examined with 19 fungal isolates from the rhizo-spheric soil of plants naturally growing at a zinc mine area [62]. The Aspergillus aeneus isolate had a high zinc tolerance and potential for the extracellular synthesis of ZnO NPs. The result was the synthesis of spherical NPs (100–140 nm) coated with proteins, which served as stabilizers.

2.5. Myco-Synthesis of Nanoparticles of Other Elements

Fungal cultures can form oxides of many elements other than copper, iron, titanium, and zinc. These include magnesium, manganese, cobalt, nickel, zirconium, selenium, tellurium, silicon, cerium, silver, aluminium, bismuth, antimony, gadolinium, and ruthenium (Table 5). Many of these elements remain barely explored in terms of NP myco-synthesis, and their formation by fungal cultures has so far been described only in a few reports.
Table 5. Myco-synthesis of nanoparticles of other elements.
NP Species Source Precursors Shape and Size Reference
Al2O3 Colletotrichum sp. Mycelial extract AlCl3 Spherical (average size of 30 nm) [79]
AgO Aspergillus terreus Culture liquid AgNO3 Irregular spherical (60–100 nm) [80]
Bi2O3 Fusarium oxysporum Bio-mass Bi(NO3)3 Quasi-spherical (5–8 nm) [81]
CeO2 Aspergillus niger Culture liquid CeCl3 Spherical (5–20 nm) [82]
CeO2 Aspergillus terreus Mycelial extract Ce(NO3)3 Spherical (average size of 28.5 nm) [83]
CeO2 Fusarium solani Culture liquid CeCl3 Spherical (20–30 nm) [84]
CeO2 Humicola sp. Bio-mass Ce(NO3)3 Spherical (12–20 nm) [85]
CeO2 Talaromyces prupureogenus Mycelial extract Ce(NO3)3 Nano-sponges (average size of 21.4 nm) [83]
Co3O4 Aspergillus brasiliensis Mycelial extract CoSO4 Quasi-spherical (20–27 nm) [86]
Co3O4 Aspergillus nidulans Bio-mass Co(C5H7O2)2 Spherical (average size of 20.29 nm) [87]
Co3O4 Aspergillus terreus Culture liquid CoSO4 Spherical [16][17]
Gd2O3 Humicola sp. Bio-mass GdCl3 Quasi-spherical (3–8 nm) [88]
MgO Agaricus bisporus Fruit body extract Mg(CH3COO)2 29.6–38.6 nm [89]
MgO Aspergillus niger Culture liquid MgCl2 Spherical (40–95 nm) [90]
MgO Aspergillus tubingensis Mycelial extract Mg(NO3)2 Spherical (average size of 5.8 nm) [91]
MgO Trichoderma viride Culture liquid MgCl2 45.12–95.37 nm [92]
MnxOy Cladosporium halotolerans Living culture MnCl2 Needle-like (2–6 nm in diameter, 0.1–1 μm in length) [93]
Mn5O8 Fusarium oxysporum Bio-mass (CH3CO2)2Mn· Quasi-spherical (8–13 nm) [94]
NiO Aspergillus aculeatus Dead bio-mass NiCl2 Spherical (average size of 5.89 nm) [95]
NiO Aspergillus terreus Culture liquid NiSO4 Spherical [16][17]
NiO Hypocrea lixii Dead bio-mass NiCl2 Average size of 3.8 nm for extracellular and 1.25 nm for intracellular NPs [96]
RuO2 Fusarium oxysporum Bio-mass RuCl3 Spherical (2–5 nm) [97]
Sb2O3 Saccharomyces cerevisiae Fungal culture SbCl3 Spherical (2–10 nm) [98]
SeO2 Trichoderma harzianum Living culture Na2SeO3 – [99]
SiO2 Fusarium oxysporum Bio-mass K2SiF6 Quasi-spherical (5–15 nm) [47]
SiO2 Fusarium oxysporum Bio-mass Amorphous silica present in rice husk Quasi-spherical (2–6 nm) [100]
SiO2 Saccharomyces cervisiae Living culture Sodium silicate Spherical (40–70 nm) [101]
TeO2 Mortierella humilis Living culture Na2TeO3 – [99]
TeO2 Trichoderma harzianum Living culture Na2TeO3 – [99]
ZrO2 Fusarium oxysporum Bio-mass K2ZrF6 Quasi-spherical (3–11 nm) [102]
ZrO2 Fusarium solani Culture liquid zirconyl nitrate Spherical (40–50 nm) [103]
ZrO2 Penicillium aculeatum Culture liquid ZrCl4 Spherical (average size of 39.32 nm) [104]
ZrO2 Penicillium notatum Culture liquid ZrCl4 Spherical (average size of 62.27 nm) [104]
ZrO2 Penicillium purpurogenome Culture liquid ZrCl4 Spherical (average size of 53.60 nm) [104]
Several research groups were able to prepare mycogenic NPs of cerium oxide. CeO2 nanospheres (5–20 nm) have been successfully obtained with an A. niger culture liquid filtrate [82]. The NPs showed a high antibacterial activity against pathogenic bacteria and larvicidal and pupicidal activity against mosquito vectors. Spherical 20–30-nm CeO2 NPs obtained with F. solani culture liquid showed a good antibacterial and antibiofilm activity against Psedomonas aeriginosa, Klebsiella pneumoniae, Escherichia coli, and Staphylococcus aureus [84].
Electrochemical analysis shows that mycogenic NPs can be used in applications such as sensors, batteries, and supercapacitors. The bio-mass of the fungus Humicola sp. was able to extracellularly form highly stable, water-dispersible, and highly fluorescent CeO2 NPs [85]. These NPs were spherical, were 12–20 nm in diameter, and were naturally capped by proteins secreted by the fungus. Komal et al. synthesized morphologically different CeO2 NPs with mycelial extracts from two fungi, A. terreus and Talaromyces prupureogenus [83]. Pure CeO2 NPs synthesized with A. terreus were spherical, with an average size of 28.5 nm. CeO2 NPs formed by T. pupureogenus had a unique nano-sponge morphology and an average size of 21.4 nm. The nano-sponges were more active against Candida albicans than were spherical CeO2 NPs.

3. Myco-Synthesis of Chalcogenide Nanoparticles

Chalcogens are chemical elements from group 16 of the periodic table: oxygen, sulfur, selenium, tellurium, polonium, and livemorioum. Oxygen is often treated separately from the other group 16 elements, or even excluded from the scope of the term “chalcogen”, owing to its very different chemical behavior from the other chalcogens [105]. Chemical compounds consisting of at least one chalcogen anion and at least one more electropositive element are called chalcogenides. The three most important groups of chalcogenides are sulfides, selenides, and tellurides. In recent years, fungi-assisted synthesis of chalcogenide NPs and nanomaterials has become of interest.

3.1. Myco-Synthesis of Sulfide Nanoparticles

Fungi-mediated synthesized sulfide NPs are the most commonly studied of all chalcogenides. One of the most important types of semiconductor nanomaterials with a wide band gap and with stability than that of the other chalcogenide NPs, sulfide NPs are more suitable for industrial applications, including high temperature operations, high voltage optoelectronic devices, and as high efficiency electric energy transformers and generators [106].
According to the data so far, fungal cultures can synthesize cadmium, zinc, and lead sulfide NPs. Several researchers have also found that some fungi can produce gold, silver, and copper sulfide NPs (Table 6).
Table 6. Myco-synthesis of sulfide nanoparticles.
NP Species Source Precursors Shape and Size Reference
α-Ag2S Humicola sp. Mycelial bio-mass AgNO3, Na2SO3 Spherical (15–40 nm) [107]
Au2S Humicola sp. Mycelial bio-mass HAuCl4, Na2SO3 Spherical (20–30 nm) [108]
CdS Aspergillus niger Mycelial bio-mass CdCl2, Na2S Spherical (2.7–7.5 nm) [109]
CdS Candida glabrata Living culture Cd(NO3)2 – [110]
CdS Fusarium oxysporum Living culture CdSO4 5–20 nm [111]
CdS Fusarium oxysporum Mycelial bio-mass Cd(NO3)2, sulfur waste Spherical (average size of 6 nm) [112]
CdS Fusarium sp. Mycelial bio-mass CdSO4 Spherical (80–120 nm) [113]
CdS Phanerochaete chrysosporium Living culture Cd(NO3)2 Average size of 2.56 nm [114]
CdS Pleurotus ostreatus Mycelial bio-mass CdSO4, Na2S Spherical (4–5 nm) [115]
CdS Rhizopus stolonifer Mycelial bio-mass CdCl2, ZnS Average size of 8.8 nm [116]
CdS Saccharomyces cerevisiae Living culture CdS solution Spherical (average size of 3.57 nm) [117]
CdS Saccharomyces cerevisiae Bio-mass CdCl2, Na2S Spherical (average size of 2 nm) [118]
CdS Schizosaccharo-myces pombe Living culture CdSO4 Average size of 1.8 nm [119]
CdS Schizosaccharo-myces pombe Living culture CdSO4 1–1.5 nm [120]
CdS Schizosaccharo-myces pombe Living culture Cd(NO3)2 – [110]
CdS Termitomyces heimii Fruit body extract Cd(NO3)2, Na2S Spherical (3–5 nm) [121]
CdS Trametes versicolor Living culture Cd(NO3)2 Spherical (average size of 6 nm) [122]
CdS Trichoderma harzianum Mycelial bio-mass CdCl2, Na2S Spherical (3–8 nm) [123]
CdS Trichosporon jirovecii Living culture CdCl2 Spherical (6–15 nm) [124]
CuS Fusarium oxysporum Mycelial bio-mass CuSO4 Spherical (2–5 nm) [125]
CuS Fusarium oxysporum Mycelial bio-mass Copper mine wastewaters 10–40 nm [126]
PbS Aspergillus flavus Living culture Pb(C2H3O2)2, Na2S 35–100 nm [127]
PbS Rhodosporidium diobovatum Bio-mass Pb(NO3)2 Spherical (2–5 nm) [128]
PbS Saccharomyces cerevisiae Living culture Pb(C2H3O2)2, Na2S Spherical (0.667–6.95 nm) [129]
PbS Torulopsis sp. Living culture Pb(NO3)2 2–5 nm [130]
ZnS Agaricus bisporus Fruit body extract ZnCl2, Na2S Almost spherical (2.1–3.5 nm) [131]
ZnS Aspergillus flavus Mycelial bio-mass ZnSO4 Spherical (average size of 18 nm) [132][133]
ZnS:Gd Aspergillus flavus Mycelial bio-mass ZnSO4, Gd(NO3)2 Spherical (10–18 nm) [134]
ZnS Aspergillus sp. Mycelial bio-mass ZnSO4 Spherical (average size of 11.08 nm) [135]
ZnS Fusarium oxysporum Mycelial bio-mass ZnSO4 Spherical (average size of 42 nm) [136]
ZnS Penicillium sp. Mycelial bio-mass ZnSO4 Spherical (average size of 6.3 nm) [137]
ZnS Pleurotus ostreatu Fruit body extract ZnCl2, Na2S Almost spherical (2.1–3.5 nm) [138]
ZnS Saccharomyces cerevisiae Bio-mass ZnSO4 Spherical (30–40 nm) [139]

3.2. Myco-Synthesis of Selenide Nanoparticles

Selenides are another important class of chalcogenide semiconductors. Their potential applications include photocatalysis, bioimaging and biolabeling, and nanomedicine [140]. Mycogenic selenide NPs obtained by bio-nanotechnologists so far include cadmium, lead, silver, gold, indium, and neodymium selenides. To date, they have been obtained mostly with fungal bio-mass or living cultures (Table 7).
Table 7. Myco-synthesis of selenide nanoparticles.
NP Species Source Precursors Shape and Size Reference
Ag2Se Saccharomyces cerevisiae Living culture AgNO3, Na2SeO3 Average size of 3.9 nm [141]
AuSe Fusarium oxysporum Mycelial bio-mass HAuCl4, SeCl4 Spherical (average size of 52 nm) [142]
CdSe Candida utilis Living culture CdCl2, Na2SeO3 Average size of 4.38 nm [143]
CdSe Fusarium oxysporum Mycelial bio-mass CdCl2, SeCl4 Average size of 11 nm [144]
CdSe Helminthosporum solani Mycelial bio-mass CdCl2, SeCl4 Spherical, cubic (average size of 5.5 nm) [145]
CdSe Rhodotorula mucilaginosa Bio-mass CdCl2,
Na2SeO3		 Average size of 3.2 nm [146]
CdSe Saccharomyces cerevisiae Living culture CdCl2, Na2SeO3 15–20 nm [147]
CdSe Saccharomyces cerevisiae Living culture CdCl2, Na2SeO3 Average size of 2.8 nm [148]
CdSe Saccharomyces cerevisiae Bio-mass CdCl2, Na2SeO3 – [149]
InSe Aspergillus niger Living culture InCl3, Na2SeO3 <10 nm [150]
Nd2Se3 Fusarium oxysporum Fungal nitrate-dependent reductase NdCl2, SeCl4 Spherical (average size of 18 nm) [151]
PbSe Aspergillus terreus – – Nanorods (average size of 59 nm) [152]
PbSe Trichoderma sp. Mycelial bio-mass Pb(NO3)2, SeO2 Cubic (10–30 nm) [153]
The most widely studied mycogenic selenide NPs are cadmium selenide (CdSe) NPs, and their synthesis with yeasts is the best studied so far [143][146][147][148][149][154]. Various conditions for CdSe QD synthesis with S. cerevisiae were investigated and optimized to obtain particles with a controllable size and with tunable fluorescence emission [147]. Brooks and Lefebvre examined the ability of S. cerevisiae sequentially treated with sodium selenite and cadmium chloride to synthesize CdSe QDs in the cytoplasm [148]. They optimized biosynthesis conditions for the highest yield of QDs, and through the optimized method they obtained fluorescent QDs with an average particle diameter of 2.8 nm. Shao et al. studied Se precursors and Se metabolic flux in the synthesis of CdSe QDs in S. cerevisiae and improved their ability to synthesize CdSe QDs through gene modification [149]. They identified selenocysteine as the primary Se precursor in the intracellular biosynthesis of CdSe QDs. Further studies showed that the seleno-methionine-to-selenocysteine pathway regulates CdSe QD biosynthesis. Seleno-methionine synthesis was enhanced by overexpression of the MET6 gene, and the yield of CdSe QDs in the engineered cells was increased.

3.3. Myco-Synthesis of Telluride Nanoparticles

Yet another group of chalcogenides consists of the tellurides, which also show outstanding properties and potential applications in optical, electronic, thermoelectrical, energy storing, catalytic, magnetic, and biological fields [155][156]. Their antimicrobial and anticancer properties allow them to be used in nanomedicine [157]. The fungal synthesis of NPs of these compounds has been poorly studied and has been described by only a few researchers (Table 8).
Table 8. Myco-synthesis of telluride nanoparticles.
NP Species Source Precursors Shape and Size Reference
CdTe Fusarium oxysporum Mycelial bio-mass CdCl2, TeCl4 Spherical (15–20 nm) [158]
CdTe Rhizopus stolonifer Mycelial bio-mass CdCl2, TeCl4 QDs (average size of 7.6 nm) [119]
CdTe Saccharomyces cerevisiae Living culture CdCl2, Na2TeO3 QDs (2.0–3.6 nm) [159]
InTe Aspergillus niger Living culture InCl3, K2TeO3 <10 nm [150]
The ability to fabricate CdTe NPs has been found in several species of micro-mycetes. Highly fluorescent biocompatible CdTe QDs capped with proteins were synthesized with S. cerevisiae cells [159]. The synthesized QDs, obtained after 8 days of incubation, were well-dispersed particles with a uniform diameter of about 3.6 nm. When the incubation time was shortened to 2 days, the resulting CdTe QDs were smaller (about 2.2 nm). The CdTe QDs obtained with F. oxysporum mycelial bio-mass were also highly fluorescent and were stable and biocompatible [158]. These NPs were spherical, were 15–20 nm in diameter, and showed antibacterial activity against Gram-positive and Gram-negative bacteria. Biocompatible CdTe QDs with an average size of 7.6 nm were also obtained with R. stolonifer [119]. The study of the simultaneous removal of indium, selenium, and tellurium by A. niger from media showed accumulation of elementary Te NPs and indium telluride NPs within mycelial pellets [150].

This entry is adapted from the peer-reviewed paper 10.3390/biomimetics8020224

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