Department of Pharmaceutical Sciences, School of Pharmaceutical Sciences, Babasaheb Bhimrao Ambedkar University, Lucknow-226025, Uttar Pradesh, India.
Phyto Nanocomposites represents a novel class of nanomaterials with enormous potential for the multidisciplinary research in the areas of material science, biology and medicine. This article provides an extensive insight into Phyto nanocomposites with special emphasis on synthesis, characteristics and wide range of applications. Two popular forms of Phyto nanocomposites were discussed: Silver nanoparticles synthesised using phytoextracts and Chitosan-functionalized iron oxide nanocomposites. Silver Phyto nanocomposites are synthesised by combining the plant extract with silver nitrate solution, due to reduction in the valency of silver ion, colour changes which indicates the formation of silver Phyto nanocomposites. Whereas to synthesise the Chitosan-functionalized iron oxide Phyto nanocomposites, appropriate amount of chitosan is combined with a mixture of acetic acid, iron sulphate and leaf extract and on centrifugation followed by drying. The functional and structural characteristics of Phyto nanocomposites were characterised by variety of physicochemical, microscopic, chromatographic as well as spectroscopic characterization methods like XRD, FTIR, SEM, TEM. This review also includes wide range of applications of Phyto nanocomposites in a variety of industries like they can improve drug delivery in healthcare, support tissue engineering in biomedicine, clean up water sources for environmental remediation, strengthen food packaging for sustainability, increase agricultural yield, and to develop energy storage and conversion technologies. However, there are several challenges in the way, including managing evolving trends, regulatory compliance, safety assurance, and scale-up complications. These challenges appear to be overcome by cooperative efforts and creative approaches, opening the way for a day when Phyto nanocomposites will be the catalyst for long-term innovation and societal progress.
Overview:
Various aromatic plant materials have long been used as herbal medications, dietary supplements, and cosmetics. Particularly in the pharmaceutical industry, there is a high demand for phytomolecules sourced from aromatic and therapeutic plants. However, there are certain drawbacks to these phytomolecules, including poor absorption, high toxicity and other adverse effects, bioavailability, and ineffectiveness. The application of nanotechnological vehicles can get over these restrictions.[1] The environment and society have been significantly impacted by the application of nanotechnology. Compared to bulk materials, these nanomaterials displayed variations in size, activity, conductivity, shape, and many other characteristics. It is now a component of several high-changing applications, including food and water treatments, bio-applications, energy sensors, medical, and building. Different synthetic approaches, including chemical, microwave, and laser ablation procedures, have been used in recent years to create nanomaterials [2-4]. Recently, there has been a lot of focus on the creation of nanostructured composite materials, which are composed of bioactive substances embedded in an inorganic nanostructured matrix.[5]
Importance and Scope:
One promising solution to address various issues associated with Phyto molecules is nanotechnological vehicle. Owing to their capacity to carry substantial amounts of drugs and target delivery with high precision and efficiency, nanostructures as drug delivery systems have garnered significant interest. As per existing literature, the application of nanostructures in targeted medication delivery offers advantages including enhanced drug specificity and improved treatment outcomes. Lipid-based, polymeric-based, and graphene-based nanomaterials are the most often used types of nanomaterials that are created as drug carriers[6]. In this review mainly two types of Phyto nanocomposites are discussed.
SYNTHESIS
Silver Nanoparticle Synthesis: These nanoparticles were synthesised by various physicochemical methods. But there are certain problems associated with these methods which are as follows: [9]
Alternative approaches to produce nanoparticles that are less hazardous are required because of these limitations. Because of this, there is a growing need for safe, economical, and ecologically acceptable ways to create metallic nanoparticles (MNPs), which might have a variety of uses in the pharmaceutical and biomedical industries[11,12]. The various synthesis techniques for creating nanoparticles are shown below.
Figure 1: Approaches for the Synthesis of Phyto Nanocomposites
[Source: https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10574544/ [13]]
Synthesis of silver nanoparticles can be done by two approaches i.e. top-down approach and bottom-up approach, which includes various methods like physical, chemical and biological methods. The top-down approach refers to the development of the metal nanoparticles from bulk materials, while the bottom-up approach refers to the development of complex clusters and obtained nanoparticles from molecular components.
Green Synthesis:
In this method, we synthesize nanoparticles biologically. Over traditional methods like physical and chemical, green synthesis of Ag nano particle are more preferred globally due to its overall advantage over conventional methods that are as follows:
Silver Nanoparticle Synthesized Using Phytoextracts:
The green synthesis process for silver nanoparticle starts when botanical extract is added in AgNO3 solution. Over a period, shift in coloration signifies the synthesis of nanoparticles. Aqueous AgNO3, containing silver cations (Ag+), is reduced to a neutral atomic state (Ag° species) by the botanical extract or its bioactive compound acting as reducing agents. This initiates the nucleation process, subsequently, a rapid growth/expansion phase, where finer particles join to generate larger, energetically more stable nanoparticles. Ultimately, this results in different morphologies including cubic, spherical, triangular, hexagonal, pentagonal, rod-like, and wire-like forms.[17,18]
Figure 2: Green Synthesis Method for Silver Nanoparticle
[Source: https://mnsl-journal.springeropen.com/articles/10.1186/s40486-021-00131-6/figures/1]
Chitosan-Functionalized Iron Oxide Nanocomposites:
Researchers' attention has been drawn to metal oxide nanoparticles covered with a bio-organic polymers or ligands over the past decade due to their numerous potentials in the pharmaceutical and biomedical sectors. Organic polymers can be used to modify the surface of metal oxide nanoparticles to enhance their chemical, biological, and physical characteristics.[19]
Role of Chitosan:
Chitosan (CS) is among the many polymers which possess considerable attention because of its unique properties, which include low toxicity, biodegradability, biocompatibility, and antibacterial capabilities [20]. Because of its positive charge and reactive amino and hydroxyl groups, chitosan is a cationic polysaccharide biopolymer with a wide variety of biological uses.[21]
Green Synthesis of Chitosan Functionalized Iron Oxide Nanocomposite (CS/FeO NC):
Material required:
Pure Chitosan, Nutrient Broth, plant leaves (Sample)
Leaf Extraction:
Leaf portions that had just been gathered were washed with tap water and then dried. After mixing one gram of dried leaf material with one hundred millilitres of distilled water and heating it to one hundred degrees Celsius for fifteen minutes, the extracted solution was filtered and employed in the biogenic preparation of nanocomposites.
Green Synthesis:
Following the dissolution 0.5 g of Chitosan in 50 mL of 1% (v/v) acetic acid, 25 mL of 0.5 M iron (II) sulphate, and 25 mL of leaf extract, the mixture was rapidly agitated at 60°C for half an hour. Additionally, the sample was centrifuged for 10 minutes at 12,000 rpm and the final CS/FeO NC was obtained by air-drying at 80°C.
Figure 4: Green Synthesis of Chitosan Functionalized Iron Oxide Nanocomposite
[Source:https://www.mdpi.com/jcs/jcs-06-00120/article_deploy/html/images/jcs-06-00120-g001-550.jpg]
Influence of Different Factors on Synthesis of Phyto Nanocomposites:
Various factors impact the production and generation of nanostructures such as acidity levels, thermal conditions, the amount of botanical extract, time span of the reaction, silver nitrate concentration, pressure, and other elements.
The appropriate amount of plant extract improves the dimensions and morphology of nanoparticles and boosts the output.[22]
The thermal conditions of the reaction explicitly impact the dimensions and morphology of nanoparticles. It influences the speed of reaction, which in turn affects the characteristics of the nanoparticles. By adjusting the temperature, it's possible to tailor the targeted characteristics, such as dimension, morphology, development, and distribution pattern of particles.[23,24]
The synthesis rate, dimensions, and morphology of nanostructures are affected by the solution's pH[25,26]. Higher pH levels lead to an increase in nucleation centres, aiding the transition of metallic ions transitioning into their solid metal form. The acidity level also accelerates the reaction by altering the functionality of groups within the botanical extract. Singh A K et al., 2010 found that in the course of synthesis of silver nanoparticles (Ag NPs) derived from silver nitrate, utilizing glucose as the reducing agent, using sodium hydroxide as a catalyst, and starch serving as a stabilizing agent, surface plasmon resonance/oscillation (SPR) varied depending on the pH level. [27]
Reaction time plays a significant role in nanoparticle synthesis. Dwivedi et al., 2010 observed that the distinctness of UV-Visible absorption peak improved as contact time increased, with nanoparticles forming within 15 minutes and the synthesis rate peaking at 2 hours [28]. Similarly, Dubey et al., 2010 found that Ag and Au nanoparticles began forming within 10 minutes, and prolonged contact time led to sharper absorption peaks for both types of nanoparticles.
CHARACTERIZATION TECHNIQUES:
Generally, properties like size, dispersity, surface area, and shape are targeted for characterization of nanocomposites. There are various techniques available for the characterization of Phyto nanocomposites. Some of them are as follows:
Characterization Techniques for Phyto Nanocomposites:
Figure 4: Characterization techniques for Phyto nanocomposites
Ultraviolet-Visible Spectroscopy:
UV-Visible spectroscopy is essential for monitoring the conversion of silver ions (Ag+) into silver nanostructures. This technique works by measuring the absorbance of light in the UV-visible spectrum. As silver ions are reduced to nanoparticles, a distinct absorption peak, known as surface plasmon resonance, appears around 400-450 nm[29]. This peak confirms the formation of silver nanoparticles and provides information on their size and concentration, helping us ensure the nanoparticles' stability over time.[31]
Fourier Transform InfraRed Analysis:
FTIR spectroscopy aids in detecting surface functional groups of silver nanoparticles by measuring the absorbance of infrared light at various wavelengths. When the nanoparticles are capped or stabilized by plant-derived biomolecules, these molecules exhibit characteristic vibrations. By analysing the resulting FTIR spectrum, it is possible to identify specific functional groups, such as hydroxyl, carbonyl, or amine groups, confirming the presence and role of these biomolecules in stabilizing the nanoparticles. This technique characterizes surface chemistry of particles.[31]
X-Ray Diffraction Analysis (XRD):
X-Ray Diffraction (XRD) is employed to ascertain the crystalline structure of silver nanostructures. This technique involves directing X-radiation at the nanoparticles and assessing the intensity and angles of diffracted rays. The resulting diffraction pattern provides information about the crystal structure, phase, and orientation of the nanoparticles. By analysing the diffraction patterns, it is possible to confirm the crystalline nature of the nanostructures as well as identify any impurities or defects. [32]
Scanning Electron Microscopy (SEM) or Transmission Electron Microscopy (TEM):
SEM and TEM are advanced imaging methods used to observe the dimensions and morphology of silver nanoparticles. SEM operates with a concentrated electron beam to scan the exterior of the nanoparticles, producing high-resolution images that reveal their morphology and distribution. TEM, on the other hand, transmits electrons through the nanoparticles, providing detailed images of their internal structure. TEM has thousand times higher resolution than SEM.[29] These techniques help us understand the physical features of the nanoparticles, including their dimensions, morphology, and surface texture. [33]
Dynamic Light Scattering (DLS):
DLS is employed to analyse the size of dispersed silver nanoparticles by measuring the scattering of light as it passes through a colloidal solution. When light hits the nanoparticles, it is scattered in various directions, and the intensity of this scattered light fluctuates over time due to Brownian motion. By analysing these fluctuations, DLS provides data on the distribution pattern of size and hydrodynamic radius of the nanoparticles, helping us ensure their dispersion and stability in solution. [34]
Atomic Force Microscopy (AFM):
AFM is employed to examine the size and surface structure of silver nanoparticles by scanning their surface with a sharp probe. The probe interacts with the surface atoms, creating a detailed three-dimensional image of the nanoparticles. AFM provides precise measurements of the nanoparticle’s dimensions and surface roughness, giving us valuable insights into their physical properties and stability. [35]
Zeta Potential Analysis:
Zeta potential analysis measures the electrostatic potential near the surface of silver nanoparticles, providing information on their stability and surface charges. This technique involves applying an electric field to the colloidal solution and gauging the speed of the nanoparticles' movement. The zeta potential is calculated from this velocity, indicating the degree of repulsion between particles. A high zeta potential value signifies strong electrostatic repulsion, which prevents aggregation and ensures the long-term stability of the nanoparticles in dispersion. [36]
Energy Dispersive X-ray Spectroscopy (EDX or EDS):
EDX/EDS works by detecting characteristic X-rays emitted from a sample when it is hit by high-energy electrons, which allows for the elemental composition of the sample to be determined. This technique is crucial in Phyto nanocomposites for confirming the presence and distribution of key elements, such as silver in silver nanoparticles and iron in chitosan-functionalized iron oxide nanocomposites, ensuring successful synthesis and uniform distribution.[37]
Thermogravimetric Analysis (TGA):
TGA measures the change in a material’s weight as it is heated, providing information about thermal stability and composition. In Phyto nanocomposites, TGA helps assess the thermal stability of both silver nanoparticles and chitosan-functionalized iron oxide nanocomposites, evaluating the presence of organic content like chitosan or phytochemicals and their interaction with the nanoparticles.[38]
Vibrating Sample Magnetometry (VSM):
VSM measures the magnetic properties of a material by detecting the magnetization of a sample in response to an applied magnetic field. For chitosan-functionalized iron oxide nanocomposites, VSM is vital in characterizing their magnetic behaviour, which is important for applications in targeted drug delivery and magnetic separation.[39]
Superconducting Quantum Interference Device (SQUID):
SQUID is an extremely sensitive magnetometer used to measure very subtle magnetic properties. In the context of Phyto nanocomposites, SQUID is particularly useful for detecting the minute magnetic signals in chitosan-functionalized iron oxide nanocomposites, providing insights into their magnetic interactions and potential for biomedical applications.[40]
X-ray Photoelectron Spectroscopy (XPS):
XPS works by irradiating a material with X-rays and measuring the kinetic energy of emitted electrons to determine the elemental composition and chemical states on the surface. XPS is essential in Phyto nanocomposites for analysing the surface chemistry, including the oxidation states of silver in nanoparticles and the bonding environment in chitosan-functionalized iron oxide nanocomposites.[41]
Differential Scanning Calorimetry (DSC):
DSC measures heat flow into or out of a sample as it is heated or cooled, revealing phase transitions, crystallinity, and thermal properties. In Phyto nanocomposites, DSC is used to evaluate the thermal transitions of chitosan and other organic components, helping to understand their interactions with nanoparticles and their effect on the overall thermal behaviour of the composite.[42]
APPLICATIONS:
Applications of Silver Nanoparticles: AgNPs have a wide range of applications. Some of them are as follows:[43]
Neharika Kabtiyal et al., synthesized silver nanoparticle from plant extract to control the mosquito population. [44] Since its synthesis doesn't require energy and it's inexpensive and environmentally friendly [45]. This can address the serious issue those chemically manufactured pesticides bring about. It is possible to manage the mosquito population with little dose required and no environmental effect.[46] However, research in this area is still necessary to achieve a green future.
Bacteria called Staphylococcus aureus infiltrate the skin, gastrointestinal system, and bloodstream. These infections are linked to a high death rate.[47] Pathogenic E. coli strains cause infections both in the intestines and other parts of the body by releasing various harmful substances, such as adhesins, toxins, iron-acquisition factors, and lipopolysaccharides, which disrupt a wide range of cellular processes.[48] Bacillus and Pseudomonas putida are typically found in soil and water, but they can also act as opportunistic human pathogens, leading to hospital-acquired infections.[49] Therefore, inhibiting these bacteria is highly significant. Abhay Sinh Salunkhe et al., found that AgONP exhibited strong inhibitory effects against all the tested bacteria. The inhibitory activity increased with higher concentrations of the nanocomposite. [50]
Because of its superior food safety and anti-spoilage capabilities, Phyto-nano-packaging is now being utilized in the food business. Through its prolonged antibacterial and barrier capabilities, the usage of Phyto-nanomaterial-based packaging can extend the inherent features of the product, such as colour, texture, scent, and taste of the packed fruits and vegetables, hence avoiding spoiling. Numerous nanomaterials have been used over recent years to create capable, intelligent, and active packaging. This trend has encouraged the food and packaging industries to use a variety of ecologically friendly nanomaterials with low toxicity. It may be possible to use plant metabolites as effective antioxidants and antimicrobials.[51]
Despite being less biocompatible and chemically stable than AuNPs, AgNPs offer more sensitive plasmonic biosensors because of their LSPR [Localized surface plasmon resonance] characteristics. As the synthesis of AgNPs is now well understood and documented, a variety of particle forms, from the most basic to unique and unusual, may be created. The inorganic or organic coating, addresses the aforementioned concerns of stability and toxicity. Now a days gold with silver nanoparticles are used more.[52]
Particularly those made of silver or gold, metal nanoparticles have demonstrated virucidal action against a wide range of viruses and unquestionably lower the viral infectivity of cultivated cells. Most of the time, it is possible to show or speculate that there is a direct connection between the nanoparticle and the viral surface proteins. [53]
Based on the information gathered by Swati Gajbhiye et al., [54] we can say that, depending on the size of the particles, it is safe to use silver nanoparticles in cosmetic applications. Smaller particles appear to be more harmful than larger ones. Soap containing nano silver was reported to possess bactericidal and fungicidal properties and proved efficacy in treating acne and sun damaged skin.[55]
Using established procedures, the antifungal activity of pullulan and Ag nanoparticles (NP) composite films against Aspergillus Niger was assessed by Ricardo JB et al., [56]. These novel materials were created from silver hydrosols containing the polysaccharide which forms clear cast films. It was found that the presence of such AgNPs coatings inhibited fungal growth. Furthermore, SEM was used for the first time to investigate disruption of the A. Niger spore cells. The reason for this impact in the presence of the nanocomposites was the AgNPs that was spread throughout pullulan as fillers.
A significant challenge in treating diabetic retinopathy (DR) is the compromised or abnormal vascularization, which complicates drug transport across the blood-retina barrier (BRB). The effectiveness of drugs applied topically to treat the eye's posterior segment is often limited by ocular barriers. Nanoparticles (NPs) offer enhanced permeability through the BRB and exhibit excellent biocompatibility, allowing them to traverse biological barriers more effectively and improve drug bioavailability. Encapsulating drugs within NPs can enhance their solubility and retention within the vitreous humor, provide controlled drug release, and reduce degradation within the body, which may be beneficial for regenerating nerve tissue. Among the different types of NPs, silver or some of any other metal nanoparticles stand out as particularly promising for DR treatment due to their anti-angiogenic and anti-inflammatory properties.[57]
Applications of Chitosan-Functionalized Iron Oxide Nanocomposites:
The primary ingredient in bioactive scaffolds for enhanced endogenous bone repair is chitosan. Osteo-conductivity/osteo-inductivity, biodegradability, and strong biocompatibility are some of its benefits that are driving its growing popularity within bone repair applications. These CS-based scaffolds can be produced using, freeze-drying, electrospinning, 3D printing, or sol-gel methods. Because of its adaptable structure, synergistic osteogenesis can be achieved by chemically modifying and functionalizing CS with various bioactive components, such as inorganic or organic molecular nanoparticles.[58]
Badry M et al., [59] performed the evaluation of the investigated chemicals' in vitro antiproliferative activities showed that, of the four cell lines tested, HepG2 and HCT116 cells showed the highest susceptibility to apoptosis following treatment. It is discovered that the Fe3O4/CS hybrid nanocomposite exclusively had significant activity against HepG2, while the IC50 value of the NiFe2O4/CS nanocomposite targeting human hepatocellular carcinoma HepG2 and human colon cancer HCT116 cell lines is almost relative to the reference chemotherapeutic agent doxorubicin value. Considering their results, it clearly implies that NiFe2O4/CS nanocomposite deserves more research as chemotherapeutic compound for cancer.
Chitosan coated iron oxide nanocomposites reduces the risk of postharvest disease and weight loss during storage of fruits. The organic functional groups on the surface and the basal metallic core make them helpful. [60]
In drug delivery applications, chitosan nanocomposites are frequently utilized to treat a range of illnesses, such as osteoarthritis and cancer. By delivering medications to the intended location or tumour, drug-embedded nanocomposites demonstrate good pharmacokinetics and other multifunctional features. Drug release rates may be adjusted and burst drug release can be prevented using stimuli-responsiveness. Drugs can be effectively incorporated in polymers based on chitosan. One way to change the amorphous nature of the materials and affect drug loading efficiency and release properties is to chemically modify chitosan. [61]
Iron nanoparticles are effective in adsorbing both organic and inorganic materials from polluted water. Fe3O4, also known as magnetite, and Fe2O3, also known as maghemite, are the two most often utilized iron-based magnetic nanoparticles [62-64]. Adsorption, chemical reduction, and reductive precipitation are some of the oxidation states of iron that will determine the method of contaminant removal by iron-based nanoparticles.[65]
Iron oxide nanocomposites are used for the decolorization of textile water. Manganese peroxidase (MnP) is an enzyme used for degradation of organic pollutants. Siddeegs SM et al., [66] anchored the MnP on the surface of nanocomposite Fe3O4/ Chitosan. It was sourced from anthracophyllum discolor fungi. These nanocomposites provide high surface area for immobilizing the enzyme Manganese peroxidase.
CONCLUSION:
In this review, the synthesis, characterization, and diverse applications of Phyto nanocomposites were discussed, focusing on silver nanoparticles synthesized using Phyto extracts and chitosan-functionalized iron oxide nanocomposites. The green synthesis methods discussed which offer an environmentally friendly and sustainable approach to nanoparticle production, emphasizing the role of plant extracts and chitosan as stabilizing and functionalizing agents. The characterization techniques, including structural, chemical, magnetic, thermal, and optical methods, provide a comprehensive understanding of the properties and behaviour of these nanocomposites. The applications of silver nanoparticles span across biomedical, environmental, and industrial domains, showcasing their potential as antimicrobial agents, therapeutic and diagnostic tools, and in environmental remediation, particularly in water treatment. The use of these nanoparticles in cosmetics, textiles, and the food industry further highlights their versatility and industrial relevance. Overall, the integration of Phyto nanocomposites into various fields reflects their potential to address current challenges in medicine, industry, and environmental sustainability. Future research should focus on optimizing their synthesis, enhancing their functional properties, and expanding their applications to fully realize their benefits in real-world scenarios.
REFERENCE
Chimpiri Srujani , Raj Bajpai, Ananya Mishra, Shashikant Gautam, Aditya Kumar Sharma, Phyto Nanocomposites: Synthesis, Characterization & Applications, Int. J. of Pharm. Sci., 2024, Vol 2, Issue 9, 1236-1250. https://doi.org/10.5281/zenodo.13834502