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BY-NC-ND 3.0 license Open Access Published by De Gruyter October 14, 2016

The emerging roles of arthropods and their metabolites in the green synthesis of metallic nanoparticles

Agbaje Lateef, Sunday A. Ojo and Joseph A. Elegbede
From the journal Nanotechnology Reviews

Abstract

Nanotechnology has remained relevant as a multifacet discipline, which cuts across different areas of science and technology. Several successful attempts had been documented regarding the involvement of biological materials in the green synthesis of various metal nanoparticles (MeNPs) because of their eco-friendliness, cost-effectiveness, safe handling, and ultimately less toxicity as opposed to the physical and chemical methods with their concomitant problems. Biological agents, including bacteria, fungi, algae, enzymes, plants, and their extracts, have been implicated in most cases by several authors. Moreover, nanotechnology in recent times has also made an inroad for animal species, specifically arthropods and metabolites thereof to be used as excellent candidates for the green synthesis of MeNPs. The increasing literature on the use of metabolites of arthropods for the green synthesis of nanoparticles has necessitated the need to document a review on their relevance in nanobiotechnology. The review, which represents the first of its kind, seeks to underscore the importance of arthropods in the multidisciplinary subject of nanoscience and nanotechnology.

1 Introduction

Arthropods belong to the phylum Arthropoda, and this consists of the insects, arachnids, myriapods, and crustaceans. Arthropods possess distinct features, which include jointed limbs and cuticle composed of calcium carbonate and/or α-chitin [1]. There are several millions of arthropod species varying between 1,170,000 and 5–10 million, and for this reason, they account for more than 80% of all known species of living animals and approximately two thirds of currently existing species [2]. There are four major groups of arthropods: Chelicerata (horseshoe, spiders, and scorpions), Crustacea (shrimps, lobsters, and crabs), Tracheata (insects and myriapods), and the extinct trilobites, which were the first animals whose eyes were reportedly capable of high-degree resolution, with several other species that are well known [3]. It has been established that insects and other arthropods provide condiments that have been highly essential and of utmost importance in traditional medicine for many years, particularly in some parts of Africa, East Asia, and South America [4].

Natural products, which are usually secondary metabolites, and their derivatives constitute more than 50% of the drugs used clinically for the treatment of diverse ailments world over. Many of these products are produced from plants, fungi, and bacteria [5]. However, it has been reported that arthropods, being ubiquitous globally, have also played a vital role in the provision of inexpensive and abundant healing agents, most especially in countries where there are economic challenges [5]. Some of the arthropods’ natural agents include bee venom containing varieties of peptides, including adolapin, mast-cell degrading peptide, melittin, phospholipase, and nonpeptide compounds, which all have useful applications in the treatment of cancer [6], [7], [8], control of diabetes [9], treatment of neurodegenerative disease [10], treatment of free radical-mediated disease [11], and treatment against HIV infection [12].

It was also reported that enzymes such as chymotrypsin, serine proteases, metalloproteinase, and aspartyl proteinase produced by maggots (larvae of Lucilia sericata, Lucilia cuprina, Calliphora vicina, and Phormia regina) play important roles in the healing of diabetic foot wound, postoperative infections, leg ulcers, and bed sores [13], [14], [15], [16]. Furthermore, defensin, an enzyme produced by house flies alongside other factors, played an important role as an antibacterial agent against the methicillin-resistant Staphylococcus aureus (MRSA) and the vancomycin-resistant enterococci [17], [18]. Cantharidin, a toxin produced from the bodies of several species of blister beetles, has also been found as a useful therapeutic agent. It has also been used for the removal of warts [19], treatment of cancer [20], [21], [22], [23], [24], [25], [26], and prevention of apoptosis and DNA damage [27]. Polybia MPI, a novel antimicrobial peptide present in the venom of social wasp (Polybia paulista), was reported to be capable of cell membrane disruption and has also played a vital role in cancer therapy [28], [29].

Nanotechnology has continued to receive great attractions because of its widespread applications in different aspects of life endeavors. It is a subject that cuts across different fields of science and technology. The quest for nanomaterials that are environmentally benign, cost-effective, and nature-friendly has led to the green (biological) synthesis of metal nanoparticles (MeNPs) with the size range of 1–100 nm, and it is an attractive alternative to physical and chemical protocols. Several biological agents including bacteria, fungi, plants, enzymes, and extracts have been used for the biological synthesis of MeNPs [30], [31], [32], [33], [34], [35], [36], [37], [38], [39], [40], [41], [42], [43]. However, there are few reports on the biological synthesis of MeNPs using metabolites of the arthropods. This article therefore seeks to review the involvement of several arthropods in the green synthesis of MeNPs as well as their various practical applications.

2 Honey bee

In this modern age, Apis mellifera, which is commonly called western honey bee, remains one of the few species having a considerable social impact [44]. As one of the “eusocial” colonies of insects, honey bees are distinguished into two castes, the queen and the worker. The queen (usually one per colony) has the ability to procreate, whereas the workers amass food, take care of the young ones, construct the nest, and also secure the colony. Social evolution has provided the honey bee with unique characteristics [45], [46]. The queen is capable of laying up to 2000 eggs in a day and store sperm for a long period without losing its viability. Its life span is estimated to be 10 times more than that of the workers (i.e. 1–2 years) [47].

There are a million neurons found in the honey bee (four times as much as that of Drosophila but five orders of magnitude less than that of humans) according to Witthöft et al. [48]. Honey bees have the ability to learn abstract concept, which may be “same” or “different” [49]. They are holometabolous organisms belonging to the same insect order (Hymenoptera) as species of ants, sawflies, and wasps. The male bees arise from unfertilized haploid eggs, whereas the females arise from fertilized diploid eggs; hence, they exhibit haplodiploid sex determination [50], [51]. The suggested geographical regions where A. mellifera originated are Africa [45], Middle East [52], and Asia [53], and these creatures were reportedly carried by humans to all other parts of the world because of their ability to make honey [53].

3 Bee honey

For many centuries, honey as a natural product of honey bee, is renowned as a sweetening agent of mankind and is also considered as one of the healthiest foods ever known. Honey is composed of fructose and glucose as well as amino acids that help nourish the body and has been a subject of extensive study all over the world in terms of their physicochemical properties, mineral content, vitamins, and quality control [54], [55], [56], [57], [58]. According to Philip [59], it was reported that the high energy, chemical constituent, vitamins, enzymes, and important minerals such as potassium and magnesium found in the honey help to elongate the life span of man. Honey plays an important role in the repair and regeneration of tissues. For instance, the 5.8-kDa of honey component isolated by Tonks et al. [60] was reported to induce the production of tumor necrosis factor-α cytokines via TLR4 in human monocyte cultures, which enhanced the repair and regeneration of damaged tissue.

There are also several reports on the use of honey in the treatment of wound infections, bedsores, and burns [61]. In addition, the boundaries of knowledge of bees and their honey have been further extended as a result of their contributions to the advancement of nanotechnology. Following the necessity for safe, ecologically benign, and cost-effective natural agents in the synthesis of MeNPs, bees and bee honey have been used to mediate the biosynthesis of various MeNPs such as silver (Ag), gold (Au), cerium oxide (CeO), palladium (Pd), and copper oxide (Cu2O) nanoparticles (Table 1).

Table 1:

Green synthesis of metallic nanoparticles using metabolites of arthropods

MetabolitesReaction conditionsType of nanoparticlesSize (nm)ShapeApplicationsReferences
Bee honey1 ml of the honey solution (1 g/100 ml distilled water)+ammonium solution/1 mm AgNO3 (1:2); 37°C (200 rpm); 24–72 hSilver (Ag)Antibacterial[5]
Bee honey15 ml of honey solution+1 mm AgNO3; pH 8.5Silver (Ag)4Spherical[59]
Bee honey10 ml honey solution+30 ml HAuCl4; stirred; 3 hGold (Au)15Spherical[62]
Honey beePhosphate buffer treated ground bee (pH 7, 25 mm)+1 mm AgNO3+glucose; incubation (room temperature), 220 rpmSilver (Ag)12–18SphericalTreatment of colon cancer[63]
Bee honey3 ml of honey+CuCl2.H2O+NaOH (2 g)+50 ml of distilled H2O; pH 12; stirred (room temperature, 30 min)Copper oxide (Cu2O)Spherical, pyramidal, and cuboidalAntibacterial[64]
Bee honey1–5 ml of honey solution+1 ml of 1 mm HAuCl4 (added up to 10 ml with distilled H2O); room temperature; 2 hGold (Au)9.9SphericalAntibacterial and antifungal[65]
Bee honey5 ml of honey+95 ml of 0.1 m AgNO3; stirred (under bright sunlight, 10 min)Silver (Ag)Prevention of mild steel corrosion in acidic environment[66]
Bee honey50 ml of honey solution+cerium nitrate (Ce(NO3)3. 6H2O); stirred at 60°C (in oil bath); 6 hCerium (Ce)23[67]
Bee honey15 ml of honey solution+20 ml of AgNO3 (1 mm); pH 6.5–8.58Palladium (Pd)5–40Cross-coupling for the synthesis of biaryls and hydrogenation of conjugated olefins[68]
Honey and Camellia sinensis fortified with lemon5 ml of honey+50 ml of Camellia sinensis+5 ml of lemon juiceSilver (Ag)34.5Spherical[69]
Bee honey15 ml of honey solution+20 ml of 0.1 mm AgNO3; pH 6.5–8.5; 1 minSilver (Ag)11.16–14.52[70]
Cobweb extract1 ml of NaOH (0.1 m) hydrolyzed cobweb+40 ml of 1 mm AgNO3: room temperature; 8 minSilver (Ag)3–50SphericalAntibacterial, antifungal, additive in paint, and antibiotic improvement[71]
Paper Wasp-nest extract1 ml of NaOH (0.1 m) hydrolyzed nest+40 ml of 1 mm AgNO3: room temperature; 8 minSilver (Ag)12.5–95.5Anisotropic; sphere, 3D triangle, rhombus, rod, hexagonAntibacterial, antifungal, dye degradation, anticoagulant, and thrombolytic activities[72]
Silk fiberPAA modified silk+AgNO3 solution (0.02 mol/L)+UV light (365 nm); 2 hAgNPsAntibacterial activity[73]
SFAqueous SF solution+AgNO3 at pH 9–10AgNPs10Cluster with core-shell structure[74]
SFAqueous SF solution+HAuCl4; pH 9–10AuNPs29Core-shell structure[74]
RSFGraphene oxide solution+10 ml RSF solution+HAuCl4 (25 mm); pH 7; 45°C; 5 minAuNP/RGO composite10Flowerlike/monodisperseOxygen reduction reaction catalytic activity[75]
Silk filmsSilk films+1 mm HAuCl4 in 0.1 m borate buffer at pH 10.5 or H2O at pH 3 for 10 hAuNPs6Spherical/homogeneously disperse[76]
SFSF solution+CdCl2 solution+Na2S solution+ternary solution (CaCl2: H2O: C2H5OH) at 45°C for approximately 1.5 hQD-CDs/SF nanocomposite5Nearly round[77]
SFSF irradiated with electron accelerator in air (1, 5, 10, 20, and 30 kGy)WSSF-NPs40SphericalAntioxidant, ferric reducing antioxidant power assay, and synthesis of AuNPs (WSSF-NPs+HAuCl4)[78]
SFSF (0.04 wt.%)+Selenious acid solution (1 mm)+Ascorbic acid (4 mm)SeNPsSpherical/monodisperse[79]
SF10 ml SF solution+10 mg AgNO3 powder+gamma radiation (10–80 kGy)AgNPs20–40Roughly spherical with smooth edges/well dispersed[80]
SF2 ml SF-cysteine solution at pH 10+2 mm HAuCl4 at room temperatureAuNPs13±2.5MonodisperseHeterogeneous catalysis of p-nitrophenol reduction[81]
SF2 ml SF-cysteine solution at pH 10+2 mm AgNO3 at room temperatureAgNPs5±1.0MonodisperseAntibacterial activity[81]
SF2 ml SF-cysteine solution at pH 10+2 mm Na2PdCl4 at room temperaturePdNPs3±1.0[81]
SF2 ml SF-cysteine solution at pH 10+2 mm H2PtCl6 at 85°CPtNPs2±0.2[81]
SFAgNO3 powder (5–80 mg)+5 ml regenerated SF solution (1 wt.%) under light with an incandescent bulb for 2 hAgNPs12±2.1Antibacterial and biofilm inhibition activity[82]
SericinSS (5–20 mg/ml)+AgNO3 solution (1, 5, and 10 mm) at pH 9 and 11 at room temperature; constant stirring.AgNPs46–117RoundAntibacterial activity[83]
Sericin0.5 ml NaBH4 solution+100 ml AgNO3 solution (0.29 mm)+SS solutionAgNPs15Spherical/fairly monodisperseAntibacterial activities on fabric[84]

4 Bee and bee honey-mediated MeNPs

4.1 Silver nanoparticles (AgNPs)

Silver is a nontoxic inorganic material recognized for possessing an inhibitory effect toward 650 types of microbes [85], and also displays the highest electrical and thermal conductivities among all the metals [86]. AgNPs have a wide range of applications and the uppermost level of commercialization among the nanomaterials [87]. For instance, among different nanoparticles that have been investigated, AgNPs are the most promising particles that are used in the field of nanomedicine for their antimicrobial activity against several microbes [88]. Yezhelyev et al. [89] reported that AgNPs in the size range 1–100 nm is very advantageous for the diagnosis and treatment of cancers, which led to the new discipline of nano-oncology. AgNPs (not silver nanoclusters) became a member of antimicrobial silver family because of their elevated specific surface area and prominent fraction of surface atoms than bulk silver. It has also been proposed that AgNPs interact with the bacterial membranes to cause structural alteration and degradation of cells. AgNPs destroy permeability of outer membrane, hinder respiration and growth of cells, and obliterate the structure of membrane, leading to cell decomposition and death eventually [90], and may cause apoptosis through the arrest of G0/G1 cycle [91]. It has become increasingly clear that nanoparticles play prominent roles in the treatment of cancer, including the use in targeted drug delivery [92].

Singh et al. [5] demonstrated the biosynthesis of AgNPs using bee honey. Honey was boiled in deionized water and added to 1 mm concentration of silver nitrate and ammonium solution. The change in the color of the solution from bright yellow to dark brown (after 72 h of reaction) indicated the formation of nanoparticles. The biosynthesized AgNPs maximally absorbed at 420 nm when subjected to UV-Vis spectroscopy. Observation of this peak showed the extracellular reduction of Ag+ ions. The Fourier transform infrared (FTIR) spectroscopy of the AgNP solution also revealed proteins as the biomolecules responsible for the stabilization of the biosynthesized AgNPs. The AgNPs were reported to have excellent antimicrobial activity against MRSA. Moreover, following the bioreduction of the silver ions in the solution using bee honey, Philip [59] reported the synthesis of AgNPs visually characterized by the formation of golden yellow color. The biosynthesized AgNPs were characterized using analytical techniques such as UV-Vis spectroscopy, X-ray diffraction (XRD), and transmission electron microscopy (TEM). Maximum absorption at 413 nm and monodispersed spherical-shaped nanoparticles with an average size of 4 nm (as revealed by TEM) were observed. XRD revealed the biosynthesized nanoparticles as nanocrystallites, which were 6 nm in size. Although glucose in honey was suspected for the reduction process, proteins present in the honey were reportedly responsible for the stabilization of AgNPs.

El-Deeb et al. [63] investigated the involvement extract of dried bee in the synthesis of AgNPs. The extract of the honey bee was reacted with 1-mm silver nitrate as a substrate for the synthesis of the nanoparticles. There was noticeable change in color of the solution (indicating the formation of AgNPs) with maximum absorption at 450 nm. The nanoparticles were spherical with carbon, oxygen, and silver being the most prevalent elements according to TEM and energy-dispersive spectroscopic (EDX) analysis. The biosynthesized AgNPs were proposed as a promising agent in drug delivery and colon cancer therapy because of their anticolon cancer activities at both the cellular and the molecular level. In another study, Obot et al. [66] reported the formation of stable AgNPs with characteristic yellow brown color when 5 ml of bee honey was reacted with 95 ml of 0.1 m silver nitrate after exposing honey-AgNO3 solution to sunlight. The absorbance peak was found at 450 nm. The suggested reducing agent in the honey was fructose, whereas proteins were found to be responsible for the stabilization of the resulting AgNPs. The nanoparticles displayed a high level of corrosion inhibition of mild steel in 0.5 m HCl, producing an inhibition efficiency of 91.5%, with a treatment of 6% v/v of AgNPs.

Different levels of local honey from Malaysia used for the synthesis of AgNPs were reported by Haiza et al. [70]. By modulating the pH of AgNO3 and local honey as well as their concentrations, AgNPs of different morphologies were synthesized. The color of the AgNPs formed was golden yellow. As the concentration of the honey increased, the size of the nanoparticles decreased and vice versa in the range of 15.63–26.05 nm. The biosynthesized AgNPs were characterized using UV-Vis spectroscopy, FTIR, SEM, and field emission scanning electron microscope. The absorbance peaks of AgNPs at pH of 6.67, 7.00, 7.51, and 8.01 were 490, 482, 430, and 424 nm, respectively. The biosynthesized nanoparticles were anisotropic with polydispersed distribution. The reducing and stabilizing agents in the honey-AgNO3 solution were glucose and protein, respectively.

The involvement of extract of plant fortified with honey also mediated the synthesis AgNPs under sonication according to Kothai and Jayanthi [69]. The extract of Camellia sinensis fortified with lemon and honey was reacted with 0.001 m AgNO3. As the reaction proceeded, the color of the solution changed from pale yellow to reddish brown, indicating the formation of AgNPs. The analytical techniques used included UV-Vis, FTIR, EDX, and SEM. The absorbance peak was observed at 425 nm. Water-soluble alkaloids, flavonoids, and phenols were reported as the capping and stabilizing agents with elemental silver being the most prevalent in the solution. The nanoparticles formed were spherical in shape and polydispersed in distribution with the size range of 30.2–75.4 nm.

4.2 Gold nanoparticles (AuNPs)

MeNPs, particularly AuNPs, have remarkable biocompatibility and nontoxicity. Moreover, it is less oxidizable substance than silver and, thus, can be used for long-term applications. Antibodies and proteins can be conjugated to AuNPs through definite thiol functionality, which makes them significant for biochemical detection and therapeutic functions [76]. AuNPs are extensively studied because of their explicit optical, catalytic, electric, and delivery properties [93]. Uniform nanostructures with a range of morphologies have been produced, such as wires [94], spheres [95], plates [96], cubes [97], dendrites [98], and flowers [90]. It has been described that thiol moiety (–SH) can capably advance the stability and dispersity of colloidal noble MeNPs, particularly to AuNPs in solution, compared with other functional groups (–NH2, –COOH, etc.), and this is mainly because thiol (–SH) groups bind covalently to the surface of AuNPs [99]. Several reports also support the interface of thiol moiety with Ag, Pd, and Pt nanoparticles [81].

Philip [62] demonstrated the use of honey in the biosynthesis of AuNPs. Natural honey was dissolved in deionized water, and the mixture was reacted with gold chloride (HAuCl4) solution. The AuNPs formed after the bioreduction of AuCl4 were light purple in color, and the maximum absorbance of the particles was obtained at 541 nm. The sizes of the nanoparticles reduced as the quantity of the honey increased. The nanoparticles produced were anisotropic structures of sphere, rod, and triangle as revealed by TEM. Other analytical techniques used were XRD (which confirmed the crystalline nature of the biosynthesized AuNPs with an average size of ~ 15 nm) and FTIR, revealing protein as the capping and stabilization biomolecule. The nanoparticles were also suggested for therapeutic use because of their photoluminescence potentials. The AuNPs produced photoluminescence at 447 nm because of functionalization with honey.

Sreelakshmi et al. [65] reacted different volumes of honey solution (water/honey) with HAuCl4 separately, with the color of the reaction mixtures turned pale yellow at the end of the experiment, indicating the synthesis of AuNPs. Absorbance peak was observed at 550 nm. The AuNPs (diameter 9.9 nm) were spherical in shape and crystalline in nature as revealed by TEM and XRD. They also showed an excellent growth inhibition of test Gram-positive and Gram-negative bacteria, including antibiotic-resistant strains as well as Candida albicans. The MIC of 31.25 μg/ml was obtained against S. aureus MTCC 1144, whereas 62.5 μg/ml was obtained against Escherichia coli MTCC 739, Salmonella typi MTCC 733, Streptococcus mutans MTCC 890, and C. albicans MTCC 183.

4.3 Cerium oxide nanoparticles

Darroudi et al. [67] established the involvement of honey bee in the synthesis of cerium oxide nanoparticles (CeO2NPs) – a rare-earth material. The solution of honey was made by dissolving honey in distilled water. The solution was well stirred under room temperature. Cerium oxide was reacted with a clear solution in a reaction vessel placed in an oil bath at 60°C, and a light yellow color resin was obtained after stirring and was also divided into parts. Exposure to different calcinating temperatures (200–800°C) and subsequent maintenance of the product at specific temperatures in air led to the formation of CeO2NPs. The sol-gel derived CeO2NPs with aqueous honey solution as a greener capping and stabilizing agent changed from black color to lemon and finally white as a result of an increase in calcinating temperature. Absorption peak was observed at 314 nm. Other analytical techniques used included field emission electron microscope, powder XRD, energy-dispersive spectrum, FTIR, and thermogravimetric analysis. The biosynthesized CeO2NPs were approximately 23 nm and isotropic with CeO2 as the most prevalent compound in the sample. By using the neuro2A cells, the nontoxicity of the synthesized CeO2NPs at concentrations lower than 25 μg/ml was demonstrated. The study concluded that the green method could be used for the synthesis of CeO2NPs, avoiding hazardous materials/steps.

4.4 Palladium, copper oxide, and platinum nanoparticles

Reddy et al. [68] synthesized palladium nanoparticles (PdNPs) by reacting bee honey solution (water/honey) with palladium chloride (PdCl2) in acidic medium. The absorption bands of biosynthesized PdNPs at 223 and 280 nm confirmed the total reduction of Pd ions. XRD pattern showed the biosynthesized nanoparticles as crystalline solid with face-centered cubic structure. EDX result revealed strong Pd spectra with carbon and oxygen as functional entities. The nanoparticles were within the range of 5 and 40 nm according to SEM analysis. The biosynthesized PdNPs were used in Suzuki cross coupling for the synthesis of biaryls and also for the hydrogenation of conjugated olefin because of their catalytic property.

Polycrystalline copper oxide (Cu2O) is a semiconducting material used as one of the constituents of paints and as antitumor agent [100], [101]. Ali et al. [64] investigated the use of honey to mediate the synthesis of their nanoparticles. Solutions of edible honey, copper chloride dehydrate, and NaOH in distilled water were reacted together and stirred at room temperature with pH 12. However, different solvents were used to obtain the final product for comparison. The resultant Cu2O nanoparticles (Cu2ONPs) were observed to have brick red color. The nanoparticles were spherical in shape and crystalline in nature with Cu (I)-O stretching according to SEM, FTIR, and XRD analysis. The nanoparticles produced inhibited the growth of S. aureus and E. coli within 13–14 mm.

Venu et al. [102] have demonstrated the synthesis of platinum nanoparticles (PtNPs) and nanowires using honey. The reaction conducted at 100°C for 2 h led to the formation of PtNPs, having the size of ~2.2 nm, whereas at longer heating of 4–20 h, nanowires of 5–15 nm in length were obtained through the self-assemblage of PtNPs. The particles absorbed maximally at 533 nm, indicating the formation of PtNPs. The FTIR showed that particles were formed as a result of reduction by proteins through binding with carboxylate ion, whereas the XRD showed the formation of highly crystalline particles with face-centered cubic structure. The catalytic application of synthesized PtNPs was demonstrated through the synthesis of an organic dye, antipyrilquinoneimine, with the potential for detection and removal of anilines from water and soil.

5 Spiders

Spiders are creatures with four pairs of legs. They have chitinous coverings and two body regions, which are divided into cephalothorax and abdomen. The cephalothorax consists of head and thorax combined together as one external unit [103]. Of approximately 1.7 million species of bacteria, plants, animals, fungi, and protists described according to DMNS [104], the proximate figure of species of spiders in the World is 40,000 [105]. Many species of spiders construct webs, specifically the orb webs [106]. Many times, the production of silk evolved in arthropods [107]; however, spiders are recognized as notable and excellent silk craftsmen. They use different types of silk threads to form an array of structures, which range from simple lifelines to shelters for moulting, from egg sacs to webs, and also for ballooning (dynamic kitting) [108].

6 Cobweb (spider silk)

Silk can be loosely defined as fibrous proteins that are extended outside an organism body and are composed of semicrystalline molecular structures [107]. Spider silk is spun by spigots found on the spinnerets (which are three pairs of appendage-like organs) on the abdomen of the spiders. Spider silk has been reported to have unique chemical, molecular structure, and molecular properties [109]. Silk fibers produced ranked among the strongest, stretchiest, and toughest biomaterials known and are therefore common subjects of behavioral and ecological research [110].

Spiders invest physiologically important compounds in the construction of their webs. Most spider silks consist of proteins that are composed of highly repetitive amino acids “motifs”, that is, short amino acid sequence mainly consisting of highly repetitive glycine and alanine blocks [111], which is why silks are often called block copolymers. Pyrrolidine, a nonprotein compound that has hygroscopic properties, helps to keep the silk moist and also wards off ants invasion. Potassium hydrogen phosphate found in spiders produces a photon that reduces the pH to 4, thus making the silk acidic. This protects the silk from bacteria and fungi, which could otherwise digest the protein [112]. Potassium nitrate and phospholipids found in the silk are believed to prevent the protein from denaturation in the acidic milieu (surrounding) and also to prevent the growth of fungi and bacteria on it [113], [114], [115]. Other components include phosphorylated glycoprotein, pigments, and lipids, which enhance good adhesive property of the silk fiber. They are nutritionally important, and they act as a protection layer in the fiber [116], [117].

Carpathian mountain dwellers used the tubes of silk produced by a spider species, Atypus, to cover their wounds, and the silk reportedly facilitated the healing of the wounds because of its antiseptic properties [113]. Also, because the silk is rich in vitamin K, it is considered to be effective in blood clotting [118]. It was reported that the web of Nephila was used by the fishermen in the Indo-Pacific ocean to catch small fish [113]. The silk of Nephila clavipes was also used to help in mammalian neuronal regeneration [119]. At one time, spider silk was commonly used as a thread in optical devices such as telescopes, microscopes, and telescopic riffle sights. Several studies have also shown that some of bisphosphonate peptides that have antibacterial activity could be found in the spider silk [120]. Roozbahani et al. [121] evaluated the antimicrobial activity of the silk of the spider Pholcus phalangioides against food-borne bacterial pathogens. Spider cobwebs have also been used for the monitoring of pollution in industrial and residential areas [122], [123], and spiders have been used as biocontrol agents in reducing populations of insect pests on farmlands [124]. In addition, venoms of spiders have been evaluated for the treatment of cardiac arrhythmia [125], Alzheimer’s disease [126], and erectile dysfunction [127].

On the account of the combination of excellent mechanical properties, biocompatibility, and slow biodegradability, spider silk has found tremendous applications in biomedical field, such as tissue engineering [128], and also as additives in cosmetic products, such as shampoos, soaps, creams, and nail varnish, enhancing the brightness, softness, and or toughness of the products [128]. Furthermore, spider silk fibers could be applied in technical textiles (used, for example, in parachutes and bulletproof vests), which demand high toughness in combination with thinness [128]. The quest for biological material that could be used in the area of nanotechnology for the synthesis of safe, eco-friendly, and cost-effective MeNPs has further led to the exploration of spiders for the synthesis of nanoparticles.

7 Cobweb-mediated synthesis of AgNPs

In our laboratory, we have further extended the limits of knowledge on biotechnological applications of biosynthesized AgNPs through the first report of the use of spider cobweb as a novel biomaterial to synthesize AgNPs [71]. The cobweb extract obtained by alkaline hydrolysis of cobweb using NaOH under appropriate conditions was reacted with 1 mm AgNO3 solution. As the reaction (extract/AgNO3 solution) proceeded under static condition (at room temperature), a dark brown color resulting from AgNPs synthesis was formed. The biosynthesized nanoparticles were characterized using analytical techniques, including UV-Vis spectroscopy, FTIR, TEM, EDX, and selected area electron diffraction (SAED) analysis. The AgNPs produced showed a maximum absorbance at wavelength of 436 nm. The nanoparticles were crystalline in nature and spherical in shape with polydispersed distribution, and their sizes ranged between 3 and 50 nm (Figure 1). The biosynthesized nanoparticles inhibited the growth of test clinical bacterial isolates and also potentiated the activities of cefixime, augmentin, and ofloxacin to the tune of 3.9%–100%, 6.3%–100%, and 3.1–20%, respectively, against multiple drug-resistant organisms, including S. aureus, Klebsiella granulomatis, Pseudomonas aeruginosa, and E. coli (Figure 2). The AgNPs were therefore suggested as an antibacterial agent for clinical applications. The nanoparticles were also reportedly useful as an additive in emulsion paint for quality improvement and for the prevention of microbial attack, through the complete obliteration of deteriorating bacterial and fungal species that were inoculated in to the emulsion paint (Figure 3).

Figure 1: Green synthesis of AgNPs using cobweb extract and the characteristics of biosynthesized AgNPs.

Figure 1:

Green synthesis of AgNPs using cobweb extract and the characteristics of biosynthesized AgNPs.

Figure 2: The synergistic activities of cobweb extract-synthesized AgNPs with antibiotics on some clinical bacterial isolates.

Figure 2:

The synergistic activities of cobweb extract-synthesized AgNPs with antibiotics on some clinical bacterial isolates.

Figure 3: Antimicrobial activities of cobweb extract-synthesized AgNPs on bacteria and fungi inoculated into emulsion paint.

Figure 3:

Antimicrobial activities of cobweb extract-synthesized AgNPs on bacteria and fungi inoculated into emulsion paint.

8 Paper wasps

Paper wasps belonging to the genus Polistes have been studied in details among the eusocial wasps (Hymenoptera, Vespidae, and Polistinae), with the report of existence of approximately 200 cosmopolitan species [129], [130], [131]. Polistes live in groups of approximately 100 individuals per colony in nonenveloped nests. The nests are constructed on surfaces, such as twigs, leaves, dense shrubs and grass, hollow trees, and elevated natural cavities and man-made structures [132], [133]. These nests, which are paperlike, are derivatives of the eating habits of wasps on plant resources [134] and are used by female wasps as sites to lay eggs. The nests are rich in cellulose and proteins, with the reported occurrence of more than 20 amino acids obtained in field and laboratory nests; the most frequently occurring amino acids are glycine, serine, alanine, valine, and proline [135], [136], [137]. Antimicrobial metabolites, such as Dominulin A and B, have been reported from the cuticle and venom of Polistes dominulus, producing MIC of 2 and 8 μg/ml against Bacillus subtilis and E. coli [138]. However, the metabolites of paper wasps have not been adequately exploited for the green synthesis of nanoparticles.

9 Synthesis of AgNPs using hydrolyzed nest of paper wasp

We have recently reported the first study on the green synthesis of AgNPs in our laboratory using the hydrolyzed nest extract of Polistes sp. [72]. The nest was hydrolyzed with 0.1 m NaOH at a temperature of 90°C for 1 h, and the supernatant was used for the green synthesis of AgNPs without further purification (Figure 4). The crystalline AgNPs (12.5–95.55 nm) had surface plasmon resonance attained at 428 nm, with the formation of anisotropic structures of sphere, 3-D triangle, rhombus, hexagon, and rod (Figure 5). FTIR data suggest that proteins and phenolic compounds were involved in the synthesis of AgNPs. The nest extract-mediated AgNPs depicted good antimicrobial activities against K. granulomatis and P. aeruginosa in the range of 12–35 mm. Similarly, at 100 μg/ml, the AgNPs produced 100% against Aspergillus niger and Aspergillus flavus, whereas 75.61% was obtained against Aspergillus fumigatus. Furthermore, the AgNPs degraded malachite green by 64.3%–93.1% within 24 h. The biomedical application of AgNPs in the management of blood coagulation disorders was demonstrated, with the particles showing very good blood anticoagulation and clot dissolution (thrombolysis) activities in vitro (Figure 6).

Figure 4: The biosynthesis of AgNPs using paper wasp nest extract.

Figure 4:

The biosynthesis of AgNPs using paper wasp nest extract.

Figure 5: Transmission electron micrograph (A), SAED pattern (B), and EDX spectrum (C) of the biosynthesized AgNPs using nest extract of paper wasp.

Figure 5:

Transmission electron micrograph (A), SAED pattern (B), and EDX spectrum (C) of the biosynthesized AgNPs using nest extract of paper wasp.

Figure 6: Anticoagulant (A) and thrombolytic activities (B and C) of biosynthesized AgNPs. FB, fresh blood; EDTA, anticoagulant; WHA, nest extract AgNPs; BC, blood clot; S, AgNO3 solution; WH, nest extract only.

Figure 6:

Anticoagulant (A) and thrombolytic activities (B and C) of biosynthesized AgNPs. FB, fresh blood; EDTA, anticoagulant; WHA, nest extract AgNPs; BC, blood clot; S, AgNO3 solution; WH, nest extract only.

10 Silkworm and silk waste

The silkworm is the larva of the domestic silk moth Bombyx mori. It is an economically essential insect, being a principal producer of silk. Silk waste is a major part of the cocoons of silkworms (B. mori) [139]. Although it is inapt for silk textile production, the composition of such silk waste is comparable with that of good silk [140]. It is made up of fibroin core polymer (75%–83%) and sericin gluelike protein as a covering (17%–25%). The primary structure of silk fibroin (SF) polymers largely consists of the amino acid sequence of (Gly-Ala-Gly-Ala-Gly-Ser)n, existing in glycine (Gly, 43%), alanine (Ala, 30%), and serine (Ser, 12%) components [84], [141]. Fibroin and sericin are the two proteins in unprocessed silk spun from the silk glands of adult caterpillars belonging to the species B. mori. Fibroin is enclosed by the gumlike substance sericin, which composes of approximately 25% of raw silk, whereas sericin is typically removed as waste in the process of silk enhancement [142]. Both raw silk proteins have been used in the green synthesis of various MeNPs (Table 1).

11 Silk fibroin

Silk fibroin fiber (SFF) is a natural protein or biomaterial generally obtained from silkworm B. mori cocoons. It has been found that SF has unique properties for being used as healthy foods, enzyme immobilizing materials, cosmetics, cell culture medium, biosensor, artificial skin and muscle, permeable membrane, and drug release substances. It has attracted wide interest in many fields, including polymer technology, biology, materials science, medicine, sericulture, and chemical engineering, leading to the increase in studies on silk protein [143], [144], [145]. Because of its notable biocompatibility with human tissue, biodegradability, flexible morphology, drug permeability, nontoxicity, and good mechanical property [84], SF is of great significance in the field of biomedicine and applications in health care materials, such as food and cosmetic additive, tissue engineering [146], and drug delivery method [139], [147]. SF protein from B. mori silkworm is FDA permitted, and it has been used in biomedical applications, developed as scaffold materials and effectively used in healing of wounds and in tissue engineering of bone, tendon, cartilage, and ligament tissues [84], [148]. Also, it exhibits inflammatory response although less than collagen [149].

In recent times, it has been reported that SF produced from B. mori harbors antioxidant and hypolipidemic properties [150], [151]. It is of great importance as a natural antioxidant for applications in food, pharmaceutical, cosmetic, and biomedicine [152]. In investigating the interaction between silk protein and noble metal ions, the silk protein has the exceptional property to prepare nanocolloidal metal particles [153]. Water-soluble fibroin protein has 18 species of amino acid residues such as alanine, glycine, serine, and tyrosine, and it is prepared by destroying hydrogen bonds in SF and dissolving them in water [154], making them more effective in nanocolloid synthesis. This gives SFF potential to provide various reactive sites for bioinspired processes, as well as to become possible biomaterials for the synthesis of functional nanocomposites under mild conditions. SF has been used in micro- and nanoparticles for drug delivery applications [77]. The SF nanoparticles have been produced using emulsion-solvent evaporation/extraction, self-assembly, solvent displacement, phase separation, rapid expansion of supercritical solution, and spray-drying techniques [155]. Different inorganic materials such as silica, magnetite, apatite, titania, silver chloride, zirconia, and MeNPs have been deposited onto or within silk matrices to increase mechanical and optical properties [76].

SF for the synthesis of nanoparticles can be acquired by removing the outer sericin of silk fibers with anhydrous sodium carbonate solution at an appropriate temperature. SF may adapt the interface of nanoparticles, manage the growth of nanoparticles, and stabilize the nanoparticles solution [79]. Many potential applications of SF-noble metal nanocolloids, especially in biotechnology such as immunoassay, DNA identification, biosensor, and inspection, gene therapy, will gain prominence in research [74].

12 Synthesis of nanoparticles with SF

12.1 Silver nanoclusters and nanoparticles

Silk templates have been used as a matrix for the incorporation of preformed AgNPs and also for binding metal ions from solutions and their consequent chemical reduction [76]. Wang et al. [73] demonstrated the in situ growth of Ag nanoclusters on silk fibers, which resulted in a novel composite silk fiber with luminescence and strong antibacterial activities against E. coli and S. aureus. The synthesis involved soaking polyacrylic acid-modified silk into an aqueous silver nitrate solution (0.02 mol/l) and then irradiating it using 365 nm ultraviolet (UV) light lamp. Under the UV light, silk fibers transformed color from white to pink, signifying the formation of Ag nanoclusters. The characterization of the Ag nanocluster using the UV-Vis absorption spectra indicated an absorption peak of approximately 490 nm, which is associated with Agn nanoclusters (n=4–9) [156]. The fluorescence emission spectra showed strong emission band traversing from 500 to 700 nm under the excitation of 450 nm. Also, the images from confocal microscope proved that the Ag nanoclusters displayed the luminescence emission properties. The X-ray photoelectron spectroscopy (XPS) measurements showed the characteristic energy values of metallic Ag (0), signifying Ag (I) ions were reduced to Ag atoms.

Chen et al. [74] reported the synthesis of metal nanocolloid by SF solution in situ reduction in which SF acted as both reducing agent and protector. This kind of noble metal nanocolloid has a novel core-shell structure with a stable and highly dispersed nature. Aqueous SF solution was reacted with AgNO3 solution at room temperature. Ag nanocolloid synthesis was signified by the gradual change of the silver solution from a chromic into yellow after a period. The UV-Vis spectra indicated a symmetric absorption band appearing at 420 nm; the colloids were monodisperse, around spherical, and size distribution was reportedly narrow. FT-IR measurement showed peaks at 1622, 1512, and 1262 cm−1 relating to amide I, amide II, and amide III bands, respectively. Also, amide IV band was obtained at 694 and 642 cm−1. The morphology of the nanocolloid was observed using TEM, which indicated that the silver nanocolloid was formed as a cluster that has more than 10 core-shell structured silver-SF particles. The average size of the silver cores was reported as approximately 10 nm.

Recently, a gamma radiation-assisted biosynthesis of AgNPs using SF was reported by Kumar et al. [80]. Silver nitrate (AgNO3) powders were added to SF solution, and the mixture was then exposed to gamma radiation of different doses from 10 to 80 kGy. Color change from colorless to yellowish then to dark brown was observed, and the formation of the Ag NPs was established by its typical surface plasmon resonance band at approximately 424 nm in UV-Vis spectra. The FTIR spectra revealed peaks indexed as belonging to amide I, amide II, and amide III bands. The XRD analysis confirmed the nanocrystalline phase of silver with fcc crystal structure. The TEM images showed that the nanoparticles were roughly spherical in shape. Also, the results from the dynamic light scattering (DLS) study showed that the average size nanoparticles formed in SF ranged from 20 (at 60 kGy) to 40 nm (at 20 kGy), indicating that increasing the radiation dose increases the rate of reduction and decreases the particle size. Thus, the size of the AgNPs can be tuned by controlling the dose of radiation.

SF was also used as a biotemplate for the synthesis of AgNPs in situ under both incandescent light and sunlight at room temperature in a study reported by Fei et al. [82]. The AgNPs showed effective antibacterial activity against the MRSA and consequently inhibited the biofilm formation caused by the same bacterium. Moreover, it was confirmed that a matured biofilm created by the MRSA can be destroyed by the SF-AgNP composite. Silver nitrate powder was added to approximately 1 wt% regenerated SF solution, which was then exposed under the light with an incandescent bulb and incubated at room temperature for 24 h for reduction and synthesis. It was believed that SF was capable of reducing Ag+ to Ag by the redox-active nature of tyrosine residues in its chemical structure. Color change from colorless to yellow was observed, and UV-Vis spectra showed absorption peak at 440 nm with small shoulder found at 347 nm, suggesting the possible existence of different sizes and morphology of AgNPs [157]. The TEM micrograph showed that the average size of AgNPs was approximately 12 nm, and the high-resolution transmission electron microscopy image of an individual nanoparticle indicated that the d-spacing of the crystallographic plane was 0.23 nm, which agrees well with the distance of (111) lattice plane of Ag [75]. Also, EDX confirmed that the local elemental composition of the product was Ag, and SAED confirmed the single crystal nature of the synthesized AgNPs.

12.2 Gold nanoparticles

Silk was also found to condense metal ions from aqueous solution without additional reducing agents, leading to the one-step in situ synthesis of MeNPs at ambient conditions. This method was applied to SF solutions at alkaline conditions to attain colloidal core-shell gold-silk nanoparticles with high monodispersity. Silk microfibers having diameters of 2–5 μm have also been used as solid templates for the reduction of gold and silver nano- and microparticles [76]. Chen et al. [74] synthesized gold nanocolloid by reacting aqueous SF solution with HAuCl4 solution at room temperature. The synthesis of nanocolloid was indicated by the gradual change in color of gold solution from yellow to purple. The UV-Vis absorption spectra showed an absorption peak at approximately 520 nm, and pH 9–10 was observed as the best condition for reduction. Characteristic amide bands in FTIR spectra of the gold nanocolloid were reported with peaks at 1621, 1515, 1262, 1232, 697, and 615 cm−1. The TEM showed the morphology of the nanocolloid as gold colloid-SF bioconjugate of sizes ranging between 40 and 60 nm. The nanocolloid was a novel core-shell structure with gold cores (approximately 29 nm) covered by SF. The gold colloid was very stable and dispersed in nature.

Flowerlike AuNP/reduced graphene oxide (RGO) composites were produced by Shengjie et al. [154] in a simple, one-pot, environmentally friendly method with regenerated silk fibroin (RSF) as the reducing agent and adhesive for binding AuNPs and RGO. This was based on the fact that RSF can be simply and firmly absorbed onto RGO surfaces by π–π stacking and H-bonding, whereas the –NH2 and –COOH groups on RSF chains can function as nucleation sites for MeNPs. The effects of reaction time, temperature, and HAuCl4: RGO ratio on the morphology of AuNPs overloaded on RGO sheets were examined. Also, the flowerlike AuNP/RGO composite showed good catalytic performance for oxygen reduction reaction. AuNP/RGO composite was prepared by reacting 25 mm HAuCl4 solution with RGO solution at 45°C for 5 min. The UV-Vis spectra indicated various peaks depending on the temperature of synthesis. The AuNP/RGO composite prepared at room temperature exhibited peak at 528 nm, 37°C at 538 nm, and 45°C at 645 nm. The SEM image revealed that the AuNPs were nearly monodispersed in a size of 200–300 nm with rough surfaces. Enlarged image illustrated that AuNPs were flowerlike and composed of some 10-nm nanoparticles. The image from the TEM showed that the AuNPs were not arranged very compactly, resulting in possible relevance in catalysis. SAED showed diverse diffraction pattern, including (111), (200), and (220) faces, signifying the existence of defects and multiple crystal domains in the Au crystals [158]. It was ascertained that by changing reaction parameters such as reaction time, temperature, and pH, the size, shape, and crystal aggregation of the AuNPs loaded on RGO could be regulated.

A study has also established a simple and adaptable strategy to generate ultrathin nanocomposite silk films with evenly dispersed AuNPs at ambient conditions [76]. It was also established that both silk I and silk II forms were capable of metal reduction, and the reduction did not alter the initial secondary structures of silk surface layers for both silk I and silk II types. For synthesis, the silk films were immersed into 1 mm HAuCl4 solution at room temperature in 0.1 m borate buffer at pH 10.5 or into water at pH 3 for 10 h. Characterization by UV-Vis spectra showed peak at 547 nm, and FTIR spectra showed a typical amide I band (1600–1700 cm−1), which is related with C=O stretching in the protein backbone joined to the N-H bending and C=N stretching modes [159]. The major peak centered at 1644 cm−1 relates with silk I spectra. There was no difference in the spectra of both silk I and silk II before and after mineralization, signifying that gold formation did not bring about any conformational transformation in silk structures. The TEM images showed that the AuNPs were evenly distributed over the surface with diameters of approximately 6.7 nm, and the sizes of nanoparticles were approximately 7.0 nm.

Recently, Wongkrongsak et al. [78] described the synthesis of water-soluble silk fibroin nanoparticles (WSSF-NPs) using electron beam irradiation. The electron beam irradiation reduced the molecular weight of SF from 250 to 37 kDa. The synthesized WSSF-NPs irradiated with electron beam doses ranging from 1 to 30 kGy showed effective antioxidant activities with EC50 for scavenging DPPH ranging from 0.27 to 0.98 mg/ml. Also, the ferric reducing antioxidant power assay indicated that relative reducing power increased along with the increase in concentration of the WSSF-NPs. Moreover, the WSSF-NPs displayed potent reducing agent for the green synthesis of gold nanocolloid. WSSF-NPs were synthesized by irradiating the aqueous solution of SF with an electron accelerator in air at different doses of 1, 5, 10, 20, and 30 kGy. FTIR spectrum showed three major peaks at 1630 cm−1, 1520 cm−1, and 1260 cm−1 belonging to C=O (amide I), N-H (amide II), and C-N and N-H (amide III), respectively. The FTIR spectrum also showed the peaks at 3280 cm−1 interpreted as N-H stretching and the peaks at 2930 and 2960 cm−1 belonging to C-H stretching of the amino acid. SEM and TEM micrographs indicated that the WSSF-NPs were loosely packed spherical particles and they have an average diameter of approximately 40 nm. The WSSF-NPs also mediated the synthesis of gold nanocolloid by reacting 10-kGy irradiated WSSF-NPs with 0.1 mm HAuCl4 for 24 h. Color change from pale yellow to dark violet color was observed, and UV-Vis spectrum indicated various peaks for the gold nanocolloid at 545, 550, 555, and 560 nm depending on the concentration of WSSF-NPs added.

12.3 Cadmium and selenium nanoparticles

A suitable room temperature bioinspired system was developed by Su et al. [77] to synthesize hybrid quantum dot (QD)-cadmium sulphate (CdS)/SF colloid, in which SF functioned as both natural biocompatibilizer and capable passivator of trap sites on the QD-CdS surface, which could be of use in photocatalysts, novel luminescence, and photoelectron transfer devices and also for some possible usage in the biological fields. QD-CdS/SF nanocolloids consist of well-diffused QD and the substrate SFF. QD-CdS as typical II–VI semiconductor nanoparticles are studied widely because of their range of properties, including unique optical properties, photocatalytic and tunable photoluminescence with high quantum yield, and broad excitation wavelength scope [160].

For the synthesis of QD-CdS/SF nanocolloids, a certain amount of SF were dipped into CdCl2 solution, rinsed, and immersed into Na2S solution for some hours. Then it was observed that the SF changed to a yellowish color. The yellowish fibers were washed and dried in vacuum at room temperature. The yellowish solid sample gotten was immersed in the ternary solution (CaCl2:H2O:C2H5OH=1:8:2 [molar ratio]) at 45°C to dissolve the SF and to obtain a clear yellowish QD-CdS/SF colloid, which was steady at room temperature. The UV-Vis spectra characterization of the nanocolloid showed peak at 482 nm, and results of FTIR showed peaks at approximately 1645 and 1702 cm−1 (amide I bands) due to C=O stretching, at approximately 1515 cm−1 (amide II bands) due to N-H bending, and at approximately 1230 and 1261 cm−1 (amide III bands) due to vibrations involving O-C-N and N-H. Also, the peak in the region of 1645 cm−1 of the C=O stretching band shifted to 1657 cm−1, revealing the chelation between Cd2+ and C=O from peptide bonds of SFF. The photoluminescence spectra showed a smooth broad peak that centered at approximately 450 nm, which indicated the formation of energy bands that may be because of the chelation of Cd2+ with the C=O from the peptide bonds of SFF. SAED revealed that CdS has hexagonal (greenockite) structure with significant planes indexed to (101), (102), (110), and (103) of greenockite CdS. The TEM image showed that the QD-CDS/SF nanocolloids were nearly round spheres with an average diameter of approximately 5 nm.

A solution-phase approach to the synthesis of selenium nanoparticles by mixing appropriate amount of SF with selenious acid solution, with the addition of ascorbic acid solution to initiate reaction, was reported by Xia [79]. Color change from colorless to red was observed. The nanoparticles were characterized by atomic force microscopy (AFM) and X-ray techniques, and the effects of temperature and ultrasonication on the morphology of selenium nanoparticles were also discussed. AFM indicated that the nanoparticles were monodispersed uniform spherical selenium colloid particles that were enveloped by SF. Also, results from XRD indicated that the nanoparticles were amorphous. The selenium nanoparticles were also reported to be stable.

12.4 Silver, gold, platinum, and palladium nanoparticles

Furthermore, Das and Dhar [81] demonstrated the use of cysteine-modified SF as a reducing agent, stabilizing agent, and material matrix in the synthesis of noble MeNPs (Au, Ag, Pd, and Pt), which was done by a facile one-pot procedure using silk fibroin-cysteine solution (SF-SH). The integration of thiols (–SH) into SF led to the formation of almost monodispersed MeNPs. In the synthesis, the aqueous solution of SF-SH at pH 10 was added to an aqueous solution of 2 mm of metal precursor (HAuCl4, AgNO3, and Na2PdCl4) at room temperature. The same method was followed at 85°C in the case of platinum. Color changes were observed as follows: AuNPs, yellow to light purple to purple to wine red; AgNPs, colorless to blackish brown; and PdNPs, yellow to colorless. However, PtNPs were not formed at room temperature by using the same reaction procedure. The UV-Vis spectra of the synthesized Au and Ag-SF-SH conjugates showed a strong absorption band at 524 and 410 nm, respectively, which were measured to be intact after a month. For Pd and PtNPs, the absorption band of the salt vanished, and there was no peak generation that may validate the formation of zero valent MeNPs. The XRD analyses show the formation of nanoparticles with strong peaks corresponding to (111), (200), and (220) based on the face-centered cubic (fcc) structure of Au and AgNPs. For PdNPs, only peak at 200 was the major peak, and PtNPs showed 111 and 200 peaks. Also, the TEM micrograph showed that the Au and Ag, Pd, and PtNPs had narrow distribution particle size of approximately 13.0, 5.0, 3.0, and 2.0 nm, respectively. The accessibility of catalytic site of nanoparticles in these biohybrid materials was demonstrated by 4-nitrophenol reduction by using NaBH4. Moreover, the 3D porous scaffold of high mechanical strength from the Au-SF-SH and Pd-SF-SH conjugate materials was also obtained, which facilitated heterogeneous catalysis. The AgNPs composite film showed very fine antibacterial activity against E. coli. Therefore, these NP-SF conjugate materials have potential for applications in catalysis and biomedicine.

13 Sericin

Silk sericin (SS) is a water-soluble protein obtained through silk refinement. Presently, SS is regarded as a waste product from the textile industry. It is extremely hydrophilic with strong polar side chains such as hydroxyl, carboxyl, and amino groups. In recent times, SS has been widely used in biomaterial applications because of its biocompatibility, biodegradability, and antioxidative and bioactive activities [83]. It is well known that sericin proteins, as the biopolymer and biocompatible materials, have attracted a lot of research interests in fields, such as cosmetics, health care food, and biomaterials [161]. SS can be extracted from silkworm cocoons by easy process such as boiling [84], also by using high-temperature and high-pressure degumming technique [162] followed by filtration to remove fibroin fibers [83]. Sericin is gaining wide applications in recent years for the synthesis of MeNPs (Table 1).

14 Synthesis of nanoparticles using sericin

14.1 Silver nanoparticles

Yue et al. [161] also used sericin as both reducing agent and dispersing agent in the synthesis of AgNPs-sericin (AgNPS-sericin) hybrid colloid, which endowed excellent antibacterial activities, good moisture absorption ability, smooth handle, and wrinkle-resistant properties to improve wearability when embedded on a cotton fabric. The synthesis involved addition of silver nitrate solution to sericin solution (50 g/l), the pH was adjusted to 9.5, and the mixture was placed on the heating magnetic stirrer at 80°C. Color change from pale yellow to brown yellow was observed, and the UV-Vis spectra showed absorption peak at 420 nm. The dynamic light scattering (DLS) showed that the hydrodynamic diameter of AgNPs in the hybrid colloid was approximately 18 nm. Also, the TEM micrograph showed good dispersion of the spherical AgNPs, which had no apparent agglomeration after 1 month, and the XRD indicated four obvious strong peaks in the whole spectrum, which are in accordance with 111, 200, 220, and 311 crystal faces of silver microcrystal [163]. The structure and morphology of the finished cotton fabric with hybrid colloid of AgNPs-sericin was studied. The FTIR spectrum showed peak at 1556 cm−1, which was attributed to the presence of C=N stretching vibration of the imine group in the finished cotton. The XPS measurements revealed binding energy peaks at 368.2 and 374.2 eV, which are in accordance with characteristic of metallic silver. Also, EDX showed strong carbon, oxygen, and gold, silver, and nitrogen peaks as expected. For the antibacterial activities of the finished cotton, initial bacterial reductions of finished cotton fabric by hybrid colloid of Ag NPS-sericin were 99.28% and 99.06% against S. aureus and E. coli, respectively. After approximately 20 washing cycles, it displayed excellent laundering strength at levels higher than 95% for S. aureus and E. coli.

SS was also used as both reducing and stabilizing agent in the synthesis of AgNPs, as reported by Aramwit et al. [83]. Prepared sericin solution was added to the AgNO3 solution (1, 5, and 10 mm) under constant stirring at room temperature overnight. Color change from transparent to yellow was observed, and UV-Vis spectra showed maximum absorption peak at 420 nm. The FTIR spectra of the SS-capped AgNPs showed new functional groups different from the original SS, which included carboxylate (1451, 1404, and 1353 cm−1) and amine salt (830 cm−1). The new absorptions signified the hydrolysis of amide linkage into its basic structural units [164]. The carboxylate groups also acted as a weak reducing agent for the synthesis of AgNPs [165], [166], [167]. The TEM micrograph showed that the SS-capped AgNPs were round shaped, with sizes ranging from 46 to 117 nm depending on the concentration of AgNO3. The SS-capped AgNPs showed potent antibacterial activity against various Gram-positive bacteria (B. subtilis, S. aureus, and MRSA) and Gram-negative bacteria (E. coli, P. aeruginosa, and Acinetobacter baumannii).

Bhat et al. [142] used sericin for the stabilization of AgNPs synthesized by the reduction of silver nitrate with sodium borohydride in an aqueous solution, and color change from transparent to yellow was observed. The UV-Vis spectra revealed an absorption peak of 389 nm (after the synthesis) and 399 nm (after stabilization with sericin). The TEM micrograph showed that the AgNPs were spherical particles with an average diameter of 15 nm. SEM revealed that the AgNPs have fairly uniform size distribution and were fairly monodispersed. The stability of the colloidal nanoparticles was confirmed by zeta potential measurement. The nanoparticles when applied to fabric did not considerably change the color of the fabric and conferred antibacterial activities on the fabric against both Gram-positive and Gram-negative bacteria, namely, S. aureus (ATCC 6538) and Klebsiella pneumoniae (ATCC 4352).

15 Conclusion

This review has documented the relevance of arthropods in the green synthesis of MeNPs, which traverses the use of metabolites from bees, spider, silk worm, and paper wasps, among others. It is evident that arthropods possess potent biomolecules that are useful for the bioreduction of metal ions to their metallic states. The numerous bioactive molecules shown to be present in arthropods and their metabolites can serve as sources of novel materials for the green synthesis of nanoparticles, for potential applications in nanomedicine. The emerging relevance of arthropods in the green synthesis of nanoparticles is stressed in this review.

Acknowledgments

Prof. A. Lateef is grateful to the authority of LAUTECH, Ogbomoso, Nigeria, for the provision of some of the facilities used in some works cited in this review.

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Received: 2016-6-22
Accepted: 2016-8-5
Published Online: 2016-10-14
Published in Print: 2016-12-1

©2016 Walter de Gruyter GmbH, Berlin/Boston

This article is distributed under the terms of the Creative Commons Attribution Non-Commercial License, which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.

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