Chitosan nanoparticles preparation and applications - Springer Link

Environ Chem Lett (2018) 16:101–112 https://doi.org/10.1007/s10311-017-0670-y

REVIEW

Chitosan nanoparticles preparation and applications K. Divya1 · M. S. Jisha1

Received: 31 May 2017 / Accepted: 11 October 2017 / Published online: 31 October 2017 © Springer International Publishing AG 2017

Abstract Shell fish processing industry is very common in coastal areas. While processing, only the meat is taken, the head and shells are discarded as waste. On an average, the sea food industry produces 80,000 tons of waste per year. The sheer amount of waste makes degradation a slow process causing accumulation of waste over a period of time. A very simple and effective solution to this environmental hazard is the recycling of shell waste to commercially viable products like chitin. Chitosan is the N-acetyl derivative of chitin obtained by N-deacetylation. Chitosan is widely used in food and bioengineering industries for encapsulation of active food ingredients, enzyme immobilization, as a carrier for controlled drug delivery, in agriculture as a plant growth promoter. Chitosan is also a defense elicitor and an antimicrobial agent. Chitosan has interesting properties such as biodegradability, biocompatibility, bioactivity, nontoxicity and polycationic nature. This review presents structural characteristics and physicochemical properties of chitosan. The methods of preparation of chitosan nanoparticles are detailed. Applications of chitosan nanoparticles are discussed. Applications include drug delivery, encapsulation, antimicrobial agent, plant growth-promoting agent and plant protector. Keywords Chitin · Chitosan · Chitosan nanoparticles · Antimicrobial action · Agriculture

* M. S. Jisha [email protected] 1

School of Biosciences, Mahatma Gandhi University, Kerala, India

Introduction Nanoparticles range in dimension from 1 to 100 nm. They have unique properties compared to their bulk equivalents due to the decrease in dimension to atomic level (Ravishankar Rai and Jamuna Bai 2011). The properties of materials change at the nanoscale. This is because bulk materials have relatively constant properties regardless of their size, but as the size decreases, the percentage of surface atoms compared to bulk material increases. This causes unexpected properties of nanoparticles (Gupta et al. 2007). Nanoparticles are synthesized by size reduction using either top–down methods such as milling, high-pressure homogenization and sonication or bottom–up processes like reactive precipitation and solvent displacement (Vauthier et al. 2003). Nanoparticles are grouped into organic and inorganic nanoparticles. The inorganic nanoparticles have gained significant importance due to their ability to withstand adverse processing conditions (Whitesides 2003). Metal oxide nanoparticles such as titanium oxide, zinc oxide, silver oxides and magnesium oxides are of great interest among inorganic materials due to their tunable optical properties and physical and optical stability (Makhluf et al. 2005). Due to the unique electronic, metallic and structural characteristics, organic materials like carbon nanotubes, lipids and polymers have versatile applications (Hatton et al. 2008). Polymeric nanoparticles can be synthesized from natural and synthetic polymers. They are used owing to their stability and ease of surface modification. Biopolymeric nanoparticles have added advantages, like availability from marine (chitin and chitosan) or agricultural (cellulose, starch, pectin) resources, biodegradability, biocompatibility and nontoxicity. Biodegradable polymers such as chitosan are studied mainly as delivery systems for controlled release

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of active ingredients, stabilization of biological molecules like proteins, peptides or genetic material (Ghormade et al. 2011). Chitosan is a modified biopolymer, derived by partial deacetylation of chitin. It consists of alternating units of (1 → 4) linked N-acetyl glucosamine and glucosamine units. It is a white, hard, inelastic and nitrogenous polysaccharide (Badawy and Rabea 2011). Chitosan finds multifaceted applications due to its nontoxicity, biodegradability and antimicrobial properties. It is used in biomedical industries, agriculture, genetic engineering, food industry, environmental pollution control, water treatment, paper manufacture, photography and so on (Cheba 2011). Chitosan nanoparticles (ChNP) have the characteristics of chitosan and the properties of nanoparticles such as surface and interface effect, small size and quantum size effects (Ingle et al. 2008). Owing to the enormous potential of ChNP, this review explores the structural characteristics of chitosan and the different preparation methods of ChNP. Special emphasis will be placed on the application of ChNP. Chitosan‑structure and physicochemical properties Chitin was first discovered in 1811 by Henri Braconnot while conducting research in mushrooms. Later in 1859, Prof. C. Rouget found that alkali treatment of chitin yielded a substance that unlike chitin can be dissolved in acids. Hoppe Seiler called this deacetylated chitin ‘Chitosan’ (Badawy and Rabea 2011). Chitin is the wide-spread biopolymer in nature after cellulose. It is the major component of cuticles of insects, fungal cell walls, yeast or green algae (Einbu and Vayrum 2008). It is also present in crab and shrimp shells (Wang and Xing 2007). Chitosan, on the other hand, is much less abundant in nature. It has been found only in cell walls of certain fungi (Muzzarelli and Gooday 1986). Chitin is a homopolymer of β 1-4 linked N-acetyl D-glucosamine (Glc NAc; A unit) residues (Yen et al. 2009). There is mainly three classes of chitin-α, β and γ chitin. α-Chitin has antiparallel chains while β-chitin has intrasheet

Fig. 1 Structure of chitin and chitosan

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Environ Chem Lett (2018) 16:101–112

hydrogen bonding by parallel chains. γ-Chitin is a combination of α and β chitin and has parallel and antiparallel structure (Yen and Mau 2007) (Franca et al. 2008). Chitosan, obtained by deacetylation of chitin, has β 1-4 linked A unit (chitin monomer) and 2-amino 2-deoxy-β-D-glucopyranose (Glc N; D units; chitosan monomer) (Park et al. 2011; Puvvada et al. 2012; Shahidi et al. 1999). Chitosan contains at least 60% D units (Kumirska et al. 2011). The molar fraction of D units is expressed as the degree of deacetylation (DD) (Aranaz et al. 2009). The structure of chitin and chitosan is shown in Fig. 1. It is an important characteristic that influences the performance of chitosan in many applications (Kumirska et al. 2010). DD can be determined by potentiometric titration (Zhang et al. 2011), infrared radiation (Baxter et al. 1992), UV–visible spectrophotometry (Kasaai 2009), gel permeation chromatography (Kumar 1999), 1H-liquid-state NMR and solidstate 13C NMR (Ottey et al. 1996). The presence of the free amine groups along the chitosan chain makes it unlike chitin soluble in diluted acidic solvents. The molecular weight and viscosity development in aqueous solution also play a significant role in the biochemical and pharmacological application of chitosan. Other major parameters are crystallinity, ash content, moisture content, heavy metal content and so on (Rinaudo 2006). In addition to its many applications, chitosan is also an eco-friendly solution to the pollution caused by the seafood processing industry. Every year, 60,000–80,000 tons of shell waste are produced globally. This sheer amount of waste makes degradation a slow process and an environmental concern. Conversion of shell waste to chitin is an effective solution to this problem. Chitin has many applications and can also be deacetylated to form chitosan which has a myriad of applications (Divya et al. 2014). Structural modifications of chitosan Chitosan contains three functional groups; an amino group and primary and secondary hydroxyl groups at C2, C3 and C6 positions. The hydroxyl groups of chitosan make a


chemical modification by attaching side groups to the reactive hydroxyl groups without altering its biophysical properties (Rajasree and Rahate 2013). Crosslinking chitosan with glyoxal, glutaraldehyde and terephthaldehyde results in a hydrogel that can be used in organ transplants and restoring organ function (Kumar and Koh 2012). N-imidazolylO-carboxymethyl chitosan has been used for high-performance gene delivery (Shi et al. 2011a, b). Radionuclides like Ho-166, Sm-153 and Lu-166 crosslinked with chitosan are used for targeted therapy (Zolghadri et al. 2010). Chemical modification of chitosan by adding quaternary ammonium groups (Thanou et al. 2001), carboxy alkyl groups (Aiping et al. 2006) and acetic anhydrides (Hirano et al. 2002) has also been reported.

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Chitosan nanoparticles (ChNP) were first described in 1994 by Ohya and co-workers. They used ChNP prepared by emulsifying and crosslinking for intravenous delivery of anticancer drug 5-fluorouracil (Grenha 2010). Since then, many methods have been employed for the synthesis of ChNP. Five methods are presently available. They are ionotropic gelation, microemulsion, emulsification solvent diffusion, polyelectrolyte complex and reverse micellar method (Tiyaboonchai 2003). Out of this, the most widely used methods are ionotropic gelation and polyelectrolyte complex. These methods are simple and do not apply high shear force or use organic solvents (Sailaja et al. 2011). The schematic representation of different methods of ChNP synthesis is depicted in Fig. 2. Ionotropic gelation

Chitosan nanoparticle production Chitosan has the ability to form a gel on contact with anions and form beads. This property enables its use in drug delivery. But still, the large size of these beads (1–2 mm) limits its application (Shiraishi et al. 1993).

This technique was first reported by Calvo et al. (1997) and has been widely examined and developed. The method utilizes the electrostatic interaction between the amine group of chitosan and a negatively charged group of polyanion such as tripolyphosphate. Chitosan can be dissolved in acetic acid in the absence or presence of the stabilizing

Fig. 2 Schematic representation of different modes of ChNP synthesis and its various applications

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agents, such as poloxamer. Polyanion was then added, and nanoparticles were formed spontaneously under mechanical stirring at room temperature. The size and surface charge of particles can be modified by changing the ratio of chitosan to the stabilizer. A general increase in particle compactness and size was observed on increasing the chitosan concentration and on increasing the polymer to polyanion ratio (Jonassen et al. 2012). They also reported that nanoparticles dispersed in saline solution were more stable due to the smaller particle size found in the presence of sodium chloride. This is because a monovalent salt like sodium chloride when added to the solvent screens out to the electrostatic repulsion between the positively charged amine groups on the chitosan backbone. This will increase the flexibility of the polymer chains in solution and thus increase its stability (Ilium 1998). Microemulsion method This method was first reported by De et al. (1999). According to this method, a surfactant was dissolved in N-hexane and chitosan in acetic solution and glutaraldehyde was added to surfactant/hexane mixture under continuous stirring at room temperature. Nanoparticles were formed in the presence of a surfactant. The system was stirred overnight to complete the crosslinking process, between the free amine group of chitosan and glutaraldehyde. The glutaraldehyde in this method acts like a crosslinker (Fang et al. 2009). The organic solvent is then removed by evaporation under low pressure, and excess surfactant was removed by precipitate with CaCl2 and then the precipitant was removed by centrifugation. The major disadvantage of this method is the use of antigenic agent glutaraldehyde. Also, the incorporation of protein or peptides to nanoparticles is not possible as they may be damaged by the covalent crosslinking (Calvo et al. 1997). Emulsification solvent diffusion method This method was first reported by El-Shabouri (2002). It is a modified method developed by Niwa et al. (1993) employing PLGA. An emulsion is obtained upon injection of an organic phase into chitosan solution containing a stabilizing agent such as poloxamer under mechanical stirring, followed by high-pressure homogenization. The emulsion is then diluted with a large amount of water. Polymer precipitation occurs due to the diffusion of organic solvent into the water, thus forming nanoparticles. The major disadvantages of this method include the high shear forces used during nanoparticle preparation and the use of organic solvents.

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Polyelectrolyte complex (PEC) Polyelectrolyte complexes formed by self-assembly of the cationic charged polymer and plasmid DNA as a result of fall in hydrophilicity due to charge neutralization between cationic polymer and DNA. The ChNP can be spontaneously formed on addition of DNA solution into chitosan dissolved in acetic acid solution, under mechanical stirring at room temperature (Erbacher et al. 1998). Reverse micellar method This method was reported by Brunel et al. (2008). The major highlight is the absence of both crosslinker and toxic organic solvents. Also, ultrafine nanoparticles within a narrow size range can be obtained with this method. An aqueous solution of chitosan is added to the organic solvent containing surfactant under constant agitation to form reverse micelles (Zhao et al. 2011).

Preparation of chitosan nanofibers Chitosan nanofibers are solid particles with a diameter range of 1–1000 nm. Although there are many methods for nanofiber synthesis, electrospinning process has attracted attention since it produces nanofibers with a size range of micrometers to nanometers (Jayakumar et al. 2010a, b). Due to its popularity, only electrospinning process is discussed here. Chitosan gets protonated in acidic solution changing it into a polyelectrolyte. When the high electric field is applied during electrospinning, repulsive forces arise between ionic groups within the polymer, thus producing beads instead of continuous fibers. This restricts the fabrication of pure chitosan (Min et al. 2004). This problem was solved by Ohkawa and team by using trifluoroacetic acid (TFA) as a solvent. The amine groups of chitosan form salts with TFA thus eradicating the intramolecular interaction between chitosan molecules (Ohkawa et al. 2004). Acetic acid has also proved to be effective in producing chitosan nanofibers (Geng et al. 2005). Electrospinning of chitosan usually produces beads due to an inadequate stretch of filaments during the whipping of jet due to low charge density (Sun and Li 2011). To overcome this, nanofibers of blends of chitosan and synthetic polymers such as poly vinyl alcohol (PVA), poly ethyl oxide (PVO) and poly ethylene terephthalate (PET) have been produced recently (Jia et al. 2007). PVA and PEO are mainly used for biomedical applications like bone implant (Allen et al. 2004), artificial organs (Chen et al. 1994), wound dressing


(Yoshii et al. 1999), cartilage tissue repair (Sims et al. 1996), and so on. Pet is commonly used in textile and plastic industry (Sims et al. 1996).

Application of chitosan nanoparticles Chitosan nanoparticles are natural materials with excellent physicochemical, antimicrobial and biological properties, which make them a superior environmentally friendly material and they possess bioactivity that does not harm humans (Malmiri et al. 2012). Due to these unique properties, chitosan nanoparticles find a wide array of applications. Some of them are discussed below. Tissue engineering Tissue engineering is the use of living cells that have been manipulated either by genetically or by their extracellular environment, for developing biological substitutes for implantation into the body or for remodeling tissues through some active mechanism. The purpose of tissue engineering is to repair, replace, maintain or enhance the function of a particular tissue or organ (Jayakumar et al. 2010a, b). Chitosan nanoparticles, due to its biological and mucoadhesive properties, can improve transmucosal permeability, thereby enhancing transport through the paracellular pathway of the nanoparticles and can induce structural reorganization of tight junction-associated proteins (Peppas and Huang 2004). Cancer diagnosis Semiconductor nanocrystals (or quantum dots) are the most promising fluorescent probes for many biomedical applications (Jayakumar et al. 2010a, b). In spite of the success in using this nanocrystal, there arises the problem of cytotoxicity of their heavy metal composition. Chitosan nanoparticles owing to its non-toxic nature gains importance in this respect. The anticancer activity of chitosan nanoparticles can be attributed to its small size. The small particle size increases the specific surface area and surface to volume ratio which in turn increases the dissolution resulting in bioavailability of chitosan (Ghadi et al. 2014). Manjusha et al. (2010) developed folic acid (FA) conjugated carboxymethyl chitosan (CMCS) coordinated to manganese-doped zinc sulfide (ZnS: Mn) quantum dot (FACMCS-ZnS: Mn) nanoparticles which find application in targeting, controlled drug delivery and imaging of cancer cells. Anticancer drug 5-fluorouracil used for the breast cancer treatment was selected for the study. The nontoxicity, imaging, specific targeting and cytotoxicity of FA-CMCSZnS: Mn were studied.

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Drug delivery The potential use of chitosan nanoparticles as carriers has paved way for development of wide variety of colloidal delivery vehicles (Malmiri et al. 2012). Chitosan nanoparticles can cross biological barriers to protect macromolecules from degrading in biological media. It can also deliver drugs or macromolecules by controlled release to a target site (Lopez-Leon et al. 2005; Perera and Rajapakse 2013). The small size of ChNP also makes it efficient in interfacial interaction with cell membrane because the small particles will be taken up by cell by endocytosis (Ghadi et al. 2014). Several studies have been reported regarding the ability of chitosan nanoparticles to improve the bioavailability of drugs, modifying its pharmacokinetics and protecting the encapsulated drugs (Janes et al. 2001; Shi et al. 2011a, b). Apart from being used as an oral delivery carrier, ChNP can also be applied to other mucous membrane systems like pulmonary and nasal routes to deliver peptides and proteins (Fernandez-Urrusuno et al. 1999). Enzyme immobilization support Chitosan is known as an ideal material for enzyme immobilization due to its various properties like improved resistance to chemical degradation and avoiding disturbance of metal ions to an enzyme (Vazquez-Duhalt et al. 2001; Yang et al. 2010). The amino functional group of chitosan makes it suitable for enzyme immobilization (Ghadi et al. 2015). Liu et al. (2005) studied trypsin immobilized on linolenic acid-modified chitosan nanoparticles using glutaraldehyde (GA) as crosslinker and found that the thermal stability and optimum temperature of immobilized trypsin increased. Ghadi et al. (2015) reported that chitosan magnetic core shell nanoparticles are capable of immobilizing lipase enzyme. The strong bond between chitosan and lipase increases the enzyme adsorption and enzyme loading. Antioxidant activity Chitosan is a proved antioxidant agent (Rajalakshmi et al. 2013). It can scavenge free radicals and chelate metal ions by donating a hydrogen or a lone pair of electrons (Lin et al. 2009). The amino and hydroxyl functional groups of chitosan interact with metal ions triggering many activities such as adsorption, chelation and ion exchange (Onsosyen and Skaugrud 1990). The semicrystalline structure of chitosan and the strong hydrogen bonds ensures that chitosan can not be dissociated from the metal ions (Xie et al. 2001). Chitosan/fucoidan nanoparticles showed DPPH and ROS radical scavenging activity (Huang and Li 2014). Yen et al. (2008) reported that chitosan exhibited hydroxyl radical scavenging activity and iron chelating ability.

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Encapsulation of biologically active compounds Chitosan-based systems have wide and rapidly increasing applications in the food and biochemical industries. Any ingredients can be encapsulated, irrespective of it being hydrophobic, hydrophilic or bacterial (Zhao et al. 2011). Chitosan retains the bioactivity of macromolecules such as DNA and proteins during encapsulation. The positive charge of chitosan helps it to establish a strong interaction with negatively charged molecules without altering its activity (Mohammadpour Dounighi et al. 2012). Jang and Lee (2008) investigated the stability and characteristics of vitamin C-loaded chitosan nanoparticles prepared by ionic gelation of chitosan with TPP anions during heat processing in aqueous solutions. The chitosan nanoparticles were found to be heat stable, and there was a continuous release of vitamin C from chitosan nanoparticle. This indicated applicability of the system in food processing. Hu et al. (2008) investigated the process of fabricating ChNP to be used as carriers for delivering tea catechins. Sharma and Sharma (2013) reported chitosan nanoparticles showed encapsulation efficiency of 77.8% for terbinafine an antifungal agent. Water treatment Water pollution has raised serious concerns lately mainly due to the inadequacy of conventional water treatment methods. Even though, activated carbon can be used for adsorbing impurities though effective is not cost or energy efficient. The low-cost adsorbents like chitosan and cellulose are interesting options in this context (Olivera et al. 2016). The functional groups of chitosan, hydroxyl and amino groups make it an excellent absorbent and enable to be used in water

treatment for removal of functional matrices like pesticides and metal pollutants. (Dehaghi et al. 2014). Nanochitosan were tested effectively for adsorptive capacity of Pb(II) (Qi et al. 2004), Cr(VI) (Sivakami et al. 2013), Cd(II) (Seyedi et al. 2013), arsenate (Kwok et al. 2014), acid Green 27 (AG27) dye of anthraquinone type (Hu et al. 2006), etc. Chitosan nanofibers owing to their high porosity and higher surface area per unit mass are potential adsorbents. They were tested to remove Pb(II) and Cu(II) while retaining their inherent characteristics (Haider and Park 2009). ChNP-coated 4-micron membranes were tested for their drinking water purification ability in a flow through membrane filtration systems. The ChNP-coated membranes held good bacterial growth compared to noncoated membranes. Also, the filtered water showed the maximum removal of coliforms using multiple tube fermentation (MPN) test (Rajendran et al. 2015). Arafat et al. (2015) reported that chitosan zinc oxide nanoparticle composites were able to remove 99% of the color from textile effluent. Magnetic chitosan possesses good dye adsorbing capacity and can also be easily recovered from the treated water using magnetic force thus exhibiting excellent reusability (Hosseini et al. 2016). Antimicrobial agent The search for natural antimicrobials to avoid synthetic chemicals led to chitosan and chitosan nanoparticles. Table 1 gives a summary of different works done on the antimicrobial activity of ChNP. ChNP were found to be more effective against plant pathogens like Fusarium solani (Chowdappa and Gowda 2013). The antimicrobial activity of chitosan is caused by three mechanisms. The positively charged

Table 1 Antimicrobial activity of chitosan nanoparticles Compound

Organism

References

Alternaria alterneta, Macrophomia phaseolina, Rhizoctonia De Paz et al. (2011), Divya et al. (2017), Huang solani, Nigrospora sphaerica, Botryosphaerica dothidea, N. et al. (2009), Nguyen et al. (2016), Qi et al. (2004), Saharan et al. (2013), Sarwar et al. oryzae, A. tenussima, Candida albicans, Fusarium solani, (2014), Xing et al. (2016), Yien et al. (2012) Aspergillus niger, Esherechia coli, Staphylococcus aureus, Streptococcus pneumoniae, Salmonella choleraesuis, S. typhimurium, Klebsiella pneumoniae, Pseudomonas aeruginosa, Sterptococcus mutans Biofilm Chitosan microspheres E. coli, Salmonella enterica, K. pneumoniae, V. cholera, Jeon et al. (2014), Kong et al. (2008) Streptococcus uberis, S. aureus Ali et al. (2011), Chowdappa et al. (2013), Du Chitosan–silver nanoparticles E. coli, R. solani, Aspergillus flavus, A. alterneta, Collecet al. (2009), Honary et al. (2011), Kaur et al. totrichum gloesporiodies, S. aureus, Bacillus subtillus, P. (2012, 2013), Namasivayam and Roy (2013), aerugenosa Wei et al. (2009) Turmeric-chitosan nanoparticle C. albicans, Trychophytol metagrophyte, Fusarium oxyspoNguyen et al. (2014) rum, Penicillium italicum Chitosan R. solani, S. aureus, S. simulans Liu et al. (2012), Raafat et al. (2008)

Chitosan nanoparticles

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chitosan interacts with negatively charged phospholipid of plasma membrane altering the permeability of cell causing leakage of cell components and cell death. Chitosan has metal ion chelating property which is a possible cause for its antimicrobial action. There have also been reported that chitosan could penetrate the cell wall and bind to DNA inhibiting mRNA synthesis (Hernandez-Lauzardo et al. 2011; Sudarshan et al. 1992). Kaur et al. (2012) reported the fungicidal properties of nanosize silver/chitosan nanoformulations (NFs) used as an agent for antifungal treatment of seed-borne plant pathogens like Aspergillus flavus, Rhizoctonia solani and Alternaria alterneta. Ma et al. (2010) obtained chitosan nanoparticles by hydrogen peroxide degradation of chitosan. It was incorporated into antimicrobial paper by the addition of pulp, impregnation, dispersion coating on hand sheets and insufflations. It was found that the paper prepared by insufflations had the greatest activity against Escherichia coli and Staphylococcus aureus. Qi et al. (2004) evaluated the in the vitro antibacterial efficiency of ChNP and copper-loaded ChNP against E. coli, Staphylococcus choleraesuis, Salmonella typhimurium and S. aureus. The results showed that chitosan nanoparticles and copper-loaded nanoparticles inhibited the growth of all tested bacteria. Their MIC values were less than 0.25 lg/ml, and the MBC values of nanoparticles reached 1 lg/ml. Low molecular weight (LMW) ChNP and high molecular weight (HMW) ChNP have shown activity against Candida albicans, Aspergillus niger and F. solani (Yien et al. 2012). The antifungal efficacy of oleoyl-ChNP against Nigrospora sphaerica, Botryosphaerica dothidea, Nigrospora oryzae, Alternaria tenussima, Gibberella zeae and Fusarium culmorum was tested by Xing et al. (2016) and four phytopathogens N. sphaerica, B. dothidea, N. oryzae and A. Tenussima were chitosan sensitive, whereas G. zeae and F. culmorum were chitosan resistant. Chitosan silver nanoparticle composites were tested positive for its activity against mango anthracnose pathogen Collectotrichum gleosporides (Chowdappa et al. 2014). Agriculture Agricultural nanotechnology has acquired a great interest in recent times due to its ability to provide molecular management of biotic and abiotic stress, fast and easy detection of diseases, and delivery systems for fertilizers and pesticides (Kashyap et al. 2015). In spite of these advantages, selection of nanoparticles for the agricultural purpose should be exercised with caution. Since nanoparticles owing to its increased surface contact might have toxic effects absent in its bulk counterpart. It is hence advisable to use nontoxic materials for nanoparticle synthesis.

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ChNP gain its popularity in this respect (Ghormade et al. 2011). Though there are many reports of the application of chitosan in agriculture, much work has not been done using ChNP. Table 2 provides a concise list of various agricultural applications of ChNP. Chitosan has been reported to activate more than 20 pathogenesis genes like defensis, lignins, ARnase, phytoalexins, chitinase and β-gluconase and plant metabolism-related genes (Hadwiger et al. 2002). Chandra et al. (2015) reported ChNP produce significantly high defense response in Camellia sinensis by increasing the activity of defense enzymes peroxide (PO), polyphenol oxidase (PPO), phenylalanine ammonia lyase (PAL) and β-1,3-gluconase. Chitosan has a significant effect on the growth and development of various plants like rice, coffee (Van et al. 2013), wheat (Wang et al. 2015), strawberry (Saavedra et al. 2016), Dendrobium formossum orchid (Kananont et al. 2010). Chitosan also had the ability to increase chlorophyll content and nutrient uptake of plants (Van et al. 2013). ChNP have shown to impact the biophysical characteristics of coffee seedlings by increasing pigment content, the rate of photosynthesis and nutrient uptake, etc. (Dzung et al. 2011). Agricultural application of chitosan is mainly in the form of delivery systems due to its cationic properties and solubility in acidic solution (Kananont et al. 2010). The amine group of chitosan forms complex with a wide range of oppositely charged polymers (Sonia and Sharma 2011). In addition, chitosan gets easily absorbed to plant surfaces thus prolonging the contact time between plant surface and agrochemical (Tiyaboonchai 2003). Application of nanochitosan-NPK fertilizers to wheat led to significant increase in its growth performance and yield (Abdel-Aziz et al. 2016). Microspheres of chitosan and cashew tree gum were used as a carrier of Lippida sidoides essential oil to control the proliferation of insect larvae (Kashyap et al. 2015). ChNP-paraquat herbicide composite was able to reduce the herbicide toxicity (Grillo et al. 2014). Corradini et al. (2010) incorporated NPK fertilizers to methacrylic acid polymerized chitosan nanoparticles CS-PMAA. The elements were found to aggregate on the surface of chitosan nanoparticles which was indicated by the increase in mean diameter of CS-PMAA. The main reason for low agricultural productivity is environmental factors like temperature, moisture content, pests and weeds. It is therefore important to constantly monitor the plant growth. Nanosensors act as an effective evaluation mechanism by transferring nanosized biochemical and physiological changes to macrolevel (Cicek and Nadaroglu 2015). Nanochitosan biosensors with paramagnetic Fe3O4 were able to determine and remove heavy metals (Ahmed and Fekry 2013).

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Table 2 Agricultural applications of chitosan nanoparticles Compound

Crop

Use

Chitosan nanoparticles Chitosan nanoparticles Chitosan nanoparticles Chitosan nanoparticles Chitosan nanoparticles-NPK fertilizer Chitosan Chitosan Hydrolyzed chitosan Chitosan Chitosan

Robusta coffee Rice Apple Strawberry Wheat Cucumber Tobacco Rice Rice Rice

Plant growth promotion Defense against Pyricularia grisea Post-harvest protection Post-harvest protection Plant growth and yield Defense against Pythium aphanidermatum Defense against Phytophthora nicotianae Defense against Pyricularia grisea Defense/stress response activation Growth promotion and yield

Radiation degraded chitosan

Rice, red chilly, potato, carrot Carum copticum Indian spinach Maize Tomato Okra Sunflower Freesia Orchid Rose apples

Chitosan Chitosan Chitosan Chitosan Chitosan Chitosan Chitosan Chitosan Chitosan

Van et al. (2013) Manikandan and Sathiyabama (2016) Pilon et al. (2015) Hajirasouliha et al. (2012) Abdel-Aziz et al. (2016) Postma et al. (2009) Falcon-Rodriguez et al. (2011) Rodriguez et al. (2007) Agrawal et al. (2002) Van Toan and Hanh (2013), Chamnanmanoontham et al. (2015) Growth promotion and yield Dahlan et al. (2010), Yacob et al. (2013), Rekso (2008) Growth promotion and yield Mahdavi and Rahimi (2013) Growth promotion (Mondal et al. 2011) Growth promotion and yield Agbodjato et al. (2016) Growth promotion and Ralstonia wilt control Algam et al. (2010) Growth promotion and yield Mondal et al. (2012) Growth promotion and yield Cho et al. (2008) Growth promotion and yield Salachna and Zawadzińska (2014) Growth promotion and yield Nge et al. (2006) Post-harvest protection Plainsirichai et al. (2014)

Other applications The effect of different concentrations of chitosan and chitosan nanoparticles as an active coating on microbiological characteristics of fish fingers during frozen storage at − 18 °C was studied by Abdou et al. (2012). Results indicated that fish fingers coated with either chitosan or chitosan nanoparticles had much lower total bacterial count (TBC), psychrophilic bacteria, proteolytic bacteria and coliform bacteria when compared with uncoated fish fingers and that coated with a commercial edible coating. In addition, chitosan nanoparticles have been used to improve the strength and washability of textiles (Panyam and Labhasetwar 2003).

Conclusion This review summarized the preparation of chitosan nanoparticles and their various applications. From this review, it is concluded that nanostructured chitosans can be used as bioactive ingredients carriers. They have the potential to be encapsulation or immobilization carriers. Due to their favorable biological properties such as nontoxicity, biocompatibility, biodegradability and antibacterial ability, they are also interesting options as drug delivery carriers and as cell proliferation enhancers. However, most of these

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References

studies are still at the laboratory level. Additional studies are necessary before their industrial application. We hope that more chitosan nanoparticle-based application can be developed and used in the biochemical and food engineering fields and also in plant protection the near future.

References Abdel-Aziz HM, Hasaneen MN, Omer AM (2016) Nano chitosanNPK fertilizer enhances the growth and productivity of wheat plants grown in sandy soil. Span J Agric Res 14(1):0902 Abdou ES, Osheba AS, Sorour MA (2012) Effect of chitosan and chitosan-nanoparticles as active coating on microbiological characteristics of fish fingers. Int J Appl Sci Technol 2(7):158–169 Agbodjato NA, Noumavo PA, Adjanohoun A, Agbessi L, BabaMoussa L (2016) Synergistic effects of plant growth promoting rhizobacteria and chitosan on in vitro seeds germination, greenhouse growth, and nutrient uptake of maize (zea mays l.). Biotechnol Res Int 2016:1–11 Agrawal GK, Rakwal R, Tamogami S, Yonekura M, Kubo A, Saji H (2002) Chitosan activates defense/stress response (s) in the leaves of oryza sativa seedlings. Plant Physiol Biochem 40(12):1061–1069 Ahmed RA, Fekry A (2013) Preparation and characterization of a nanoparticles modified chitosan sensor and its application for the determination of heavy metals from different aqueous media. Int J Electrochem Sci 8(3):6692–6708

Environ Chem Lett (2018) 16:101–112 Aiping Z, Jianhong L, Wenhui Y (2006) Effective loading and controlled release of camptothecin by O-carboxymethylchitosan aggregates. Carbohydr Polym 63(1):89–96 Algam S, Xie G, Li B, Yu S, Su T, Larsen J (2010) Effects of paenibacillus strains and chitosan on plant growth promotion and control of ralstonia wilt in tomato. J Plant Pathol 92(3):593–600 Ali SW, Rajendran S, Joshi M (2011) Synthesis and characterization of chitosan and silver loaded chitosan nanoparticles for bioactive polyester. Carbohydr Polym 83(2):438–446 Allen MJ, Schoonmaker JE, Bauer TW, Williams PF, Higham PA, Yuan HA (2004) Preclinical evaluation of a poly (vinyl alcohol) hydrogel implant as a replacement for the nucleus pulposus. Spine 29(5):515–523 Arafat A, Samad SA, Huq D, Moniruzzaman M, Masum SM (2015) Textile dye removal from wastewater effluents using chitosan– ZnO nanocomposite. J Text Sci Eng 5(3):1 Aranaz I, Mengabar M, Harris R, Is Paos, Miralles B, Acosta N, Heras A et al (2009) Functional characterization of chitin and chitosan. Curr Chem Biol 3(2):203–230 Badawy MEI, Rabea EI (2011) A biopolymer chitosan and its derivatives as promising antimicrobial agents against plant pathogens and their applications in crop protection. Int J Carbohydr Chem 2011:1–29 Baxter A, Dillon M, Anthony Taylor KD, Roberts GAF (1992) Improved method for ir determination of the degree of n-acetylation of chitosan. Int J Biol Macromol 14(3):166–169 Brunel F, Varon L, David L, Domard A, Delair T (2008) A novel synthesis of chitosan nanoparticles in reverse emulsion. Langmuir 24(20):11370–11377 Calvo P, Remunanae-Lopez C, Vila-Jato JL, Alonso MJ (1997) Novel hydrophilic chitosan polyethylene oxide nanoparticles as protein carriers. J Appl Polym Sci 63(1):125–132 Chamnanmanoontham N, Pongprayoon W, Pichayangkura R, Roytrakul S, Chadchawan S (2015) Chitosan enhances rice seedling growth via gene expression network between nucleus and chloroplast. Plant Growth Regul 75(1):101–114 Chandra S, Chakraborty N, Dasgupta A, Sarkar J, Panda K, Acharya K (2015) Chitosan nanoparticles: a positive modulator of innate immune responses in plants. Sci Rep 5:1–14 Cheba BA (2011) Chitin and chitosan: marine biopoly-mers with unique properties and versatile applications. Glob J Biotechnol Biochem 6(3):149–153 Chen DH, Leu JC, Huang TC (1994) Transport and hydrolysis of urea in a reactor–separator combining an anion-exchange membrane and immobilized urease. J Chem Technol Biotechnol 61(4):351–357 Cho M, No H, Prinyawiwatkul W (2008) Chitosan treatments affect growth and selected quality of sunflower sprouts. J Food Sci 73(1):70–77 Chowdappa P, Gowda S (2013) Nanotechnology in crop protection: status and scope. Pest Manag Hortic Ecosyst 19(2):131–151 Chowdappa P, Kumar SM, Lakshmi MJ, Upreti K (2013) Growth stimulation and induction of systemic resistance in tomato against early and late blight by bacillus subtilis OTPB1 or trichoderma harzianum OTPB3. Biol Control 65(1):109–117 Chowdappa P, Gowda S, Chethana C, Madhura S (2014) Antifungal activity of chitosan–silver nanoparticle composite against colletotrichum gloeosporioides associated with mango anthracnose. Afr J Microbiol Res 8(17):1803–1812 Cicek S, Nadaroglu H (2015) The use of nanotechnology in the agriculture. Adv Nano Res 3(4):207–223 Corradini E, De Moura MR, Mattoso LHC (2010) A preliminary study of the incorparation of NPK fertilizer into chitosan nanoparticles. Express Polym Lett 4(8):509–515 Dahlan KZHM, Hashim K, Bahari K, Mahmod M, Yaacob N, Talip N et al (2010) Application of radiation degraded chitosan as plant

109 growth promoter. A pilot scale production and field trial study of radiation processed chitosan as plant growth promoter for rice crops. International Atomic Energy Agency de Paz LEC, Resin A, Howard KA, Sutherland DS, Wejse PL (2011) Antimicrobial effect of chitosan nanoparticles on streptococcus mutans biofilms. Appl Environ Microbiol 77(11):3892–3895 De TK, Ghosh PK, Maitra A, Sahoo SK (1999) Process for the preparation of highly monodispersed polymeric hydrophilic nanoparticles: Google Patents Dehaghi SM, Rahmanifar B, Moradi AM, Azar PA (2014) Removal of permethrin pesticide from water by chitosan–zinc oxide nanoparticles composite as an adsorbent. J Saudi Chem Soc 18(4):348–355 Divya K, Rebello S, Jisha MS (2014) A simple and effective method for extraction of high purity chitosan from shrimp shell waste. In: Proceedings of the international conference on advances in applied science and environmental engineering-ASEE Divya K, Vijayan S, George TK, Jisha M (2017) Antimicrobial properties of chitosan nanoparticles: mode of action and factors affecting activity. Fibers Polym 18(2):221–230 Du W-L, Niu S-S, Xu Y-L, Xu Z-R, Fan C-L (2009) Antibacterial activity of chitosan tripolyphosphate nanoparticles loaded with various metal ions. Carbohydr Polym 75(3):385–389 Dzung NA, Khanh VTP, Dzung TT (2011) Research on impact of chitosan oligomers on biophysical characteristics, growth, development and drought resistance of coffee. Carbohydr Polym 84(2):751–755 Einbu A, Vayrum KM (2008) Characterization of chitin and its hydrolysis to glcnac and glcn. Biomacromol 9(7):1870–1875 El-Shabouri MH (2002) Positively charged nanoparticles for improving the oral bioavailability of cyclosporin-A. Int J Pharm 249(1):101–108 Erbacher P, Zou S, Bettinger T, Steffan A-M, Remy J-S (1998) Chitosan-based vector/DNA complexes for gene delivery: biophysical characteristics and transfection ability. Pharm Res 15(9):1332–1339 Falcon-Rodriguez AB, Costales D, Cabrera JC, Martinez-Tellez MA (2011) Chitosan physico–chemical properties modulate defense responses and resistance in tobacco plants against the oomycete phytophthora nicotianae. Pestic Biochem Physiol 100(3):221–228 Fang H, Huang J, Ding L, Li M, Chen Z (2009) Preparation of magnetic chitosan nanoparticles and immobilization of laccase. J Wuhan Univ Technol Mater Sci Ed 24(1):42–47 Fernandez-Urrusuno R, Calvo P, Remuan-Lopez C, Vila-Jato JL, Alonso MJ (1999) Enhancement of nasal absorption of insulin using chitosan nanoparticles. Pharm Res 16(10):1576–1581 Franca EF, Lins RD, Freitas LCG, Straatsma TP (2008) Characterization of chitin and chitosan molecular structure in aqueous solution. J Chem Theory Comput 4(12):2141–2149 Geng X, Kwon O-H, Jang J (2005) Electrospinning of chitosan dissolved in concentrated acetic acid solution. Biomaterials 26(27):5427–5432 Ghadi A, Mahjoub S, Tabandeh F, Talebnia F (2014) Synthesis and optimization of chitosan nanoparticles: potential applications in nanomedicine and biomedical engineering. Casp J Int Med 5(3):156 Ghadi A, Tabandeh F, Mahjoub S, Mohsenifar A, Roshan FT, Alavije RS (2015) Fabrication and characterization of core-shell magnetic chitosan nanoparticles as a novel carrier for immobilization of Burkholderia cepacia lipase. J Oleo Sci 64(4):423–430 Ghormade V, Deshpande MV, Paknikar KM (2011) Perspectives for nano-biotechnology enabled protection and nutrition of plants. Biotechnol Adv 29(6):792–803 Grenha A (2010) Chitosan nanoparticles: a survey of preparation methods. J Drug Target 20(4):291–300

13

110 Grillo R, Pereira AE, Nishisaka CS, de Lima R, Oehlke K, Greiner R, Fraceto LF (2014) Chitosan/tripolyphosphate nanoparticles loaded with paraquat herbicide: an environmentally safer alternative for weed control. J Hazard Mater 278:163–171 Gupta AK, Naregalkar RR, Vaidya VD, Gupta M (2007) Recent advances on surface engineering of magnetic iron oxide nanoparticles and their biomedical applications. Nanomedicine (Lond) 2(1):23–29 Hadwiger L, Klosterman S, Choi J (2002) The mode of action of chitosan and its oligomers in inducing plant promoters and developing disease resistance in plants. Adv Chitin Sci 5:452–457 Haider S, Park S-Y (2009) Preparation of the electrospun chitosan nanofibers and their applications to the adsorption of Cu (II) and Pb(II) ions from an aqueous solution. J Membr Sci 328(1):90–96 Hajirasouliha MJM, Soheili F, Naja Fabadi (2012) Effect of novel chitosan nanoparticle coating on pot harvest qualities of strawberry. In: Proceedings of the 4th international conference on nanostructures Hatton RA, Miller AJ, Silva SRP (2008) Carbon nanotubes: a multifunctional material for organic optoelectronics. J Mater Chem 18:1183–1192 Hernandez-Lauzardo AN, Velaizquez-del Valle MG, GuerraSanchez MG (2011) Current status of action mode and effect of chitosan against phytopathogens fungi. Afr J Microbiol Res 5(25):4243–4247 Hirano S, Yamaguchi Y, Kamiya M (2002) Novel N-saturated-fattyacyl derivatives of chitosan soluble in water and in aqueous acid and alkaline solutions. Carbohydr Polym 48(2):203–207 Honary S, Ghajar K, Khazaeli P, Shalchian P (2011) Preparation, characterization and antibacterial properties of silver–chitosan nanocomposites using different molecular weight grades of chitosan. Trop J Pharm Res 10(1):69–74 Hosseini F, SadighianS Hosseini-Monfared F, Mahmoodi NM (2016) Dye removal and kinetics of adsorption by magnetic chitosan nanoparticles. Desalin Water Treat 57(51):24378–24386 Hu Z, Zhang J, Chan W, Szeto Y (2006) The sorption of acid dye onto chitosan nanoparticles. Polymer 47(16):5838–5842 Hu B, Pan C, Sun Y, Hou Z, Ye H, Zeng X (2008) Optimization of fabrication parameters to produce chitosan tripolyphosphate nanoparticles for delivery of tea catechins. J Agric Food Chem 56(16):7451–7458 Huang YC, Li RY (2014) Preparation and characterization of antioxidant nanoparticles composed of chitosan and fucoidan for antibiotics delivery. Mar Drugs 12(8):4379–4398 Huang L, Cheng X, Liu C, Xing K, Zhang J, Sun G, Chen X et al (2009) Preparation, characterization, and antibacterial activity of oleic acid-grafted chitosan oligosaccharide nanoparticles. Front Biol China 4(3):321–327 Ilium L (1998) Chitosan and its use as a pharmaceutical excipient. Pharm Res 15(9):1326–1331 Ingle A, Gade A, Pierrat S, Sonnichsen C, Rai M (2008) Mycosynthesis of silver nanoparticles using the fungus fusarium acuminatum and its activity against some human pathogenic bacteria. Curr Nanosci 4(2):141–144 Janes KA, Fresneau MP, Marazuela A, Fabra A, Alonso MJ (2001) Chitosan nanoparticles as delivery systems for doxorubicin. J Control Release 73(2):255–267 Jang K-I, Lee HG (2008) Stability of chitosan nanoparticles for l-ascorbic acid during heat treatment in aqueous solution. J Agric Food Chem 56(6):1936–1941 Jayakumar R, Menon D, Manzoor K, Nair SV, Tamura H (2010a) Biomedical applications of chitin and chitosan based nanomaterials: a short review. Carbohydr Polym 82(2):227–232 Jayakumar R, Prabaharan M, Nair S, Tamura H (2010b) Novel chitin and chitosan nanofibers in biomedical applications. Biotechnol Adv 28(1):142–150

13

Environ Chem Lett (2018) 16:101–112 Jeon SJ, Oh M, Yeo W-S, Galvao KN, Jeong KC (2014) Underlying mechanism of antimicrobial activity of chitosan microparticles and implications for the treatment of infectious diseases. PLoS ONE 9(3):92723 Jia Y-T, Gong J, Gu X-H, Kim H-Y, Dong J, Shen X-Y (2007) Fabrication and characterization of poly (vinyl alcohol)/chitosan blend nanofibers produced by electrospinning method. Carbohydr Polym 67(3):403–409 Jonassen H, Kjoniksen AL, Hiorth M (2012) Stability of chitosan nanoparticles cross-linked with tripolyphosphate. Biomacromol 13(11):3747–3756 Kananont N, Pichyangkura R, Chanprame S, Chadchawan S, Limpanavech P (2010) Chitosan specificity for the in vitro seed germination of two dendrobium orchids (asparagales: Orchidaceae). Sci Hortic 124(2):239–247 Kasaai MR (2009) Various methods for determination of the degree of n-acetylation of chitin and chitosan: a review. J Agric Food Chem 57(5):1667–1676 Kashyap PL, Xiang X, Heiden P (2015) Chitosan nanoparticle based delivery systems for sustainable agriculture. Int J Biol Macromol 77:36–51 Kaur P, Thakur R, Choudhary A (2012) An in vitro study of the antifungal activity of silver/chitosan nanoformulations against important seed borne pathogens. Int J Sci Technol Res 1:83–86 Kaur P, Choudhary A, Thakur R (2013) Synthesis of chitosan–silver nanocomposites and their antibacterial activity. Int J Sci Eng Res 4:869–872 Kong M, Chen X, Xue Y, Liu C, Yu L, Ji Q et al (2008) Preparation and antibacterial activity of chitosan microshperes in a solid dispersing system. Front Mater Sci China 2(2):214–220 Kumar MNVR (1999) Chitin and chitosan fibres: a review. Bull Mater Sci 22(5):905–915 Kumar S, Koh J (2012) Physiochemical and optical study of chitosan–terephthaldehyde derivative for biomedical applications. Int J Biol Macromol 51(5):1167–1172 Kumirska J, Mg Czerwicka, Kaczyaski Z, Bychowska A, Brzozowski K, Thaming J, Stepnowski P (2010) Application of spectroscopic methods for structural analysis of chitin and chitosan. Mar Drugs 8(5):1567–1636 Kumirska J, Weinhold MX, Thaming J, Stepnowski P (2011) Biomedical activity of chitin/chitosan based materials influence of physicochemical properties apart from molecular weight and degree of n-acetylation. Polymers 3(4):1875–1901 Kwok KC, Koong LF, Chen G, McKay G (2014) Mechanism of arsenic removal using chitosan and nanochitosan. J Colloid Interface Sci 416:1–10 Lin SB, Chen SH, Peng KC (2009) Preparation of antibacterial chito-oligosaccharide by altering the degree of deacetylation of β-chitosan in a Trichoderma harzianum chitinase-hydrolysing process. J Sci Food Agric 89(2):238–244 Liu C-G, Desai KGH, Chen X-G, Park H-J (2005) Preparation and characterization of nanoparticles containing trypsin based on hydrophobically modified chitosan. J Agric Food Chem 53(5):1728–1733 Liu H, Tian W, Li B, Wu G, Ibrahim M, Tao Z, Sun G et al (2012) Antifungal effect and mechanism of chitosan against the rice sheath blight pathogen, Rhizoctonia solani. Biotechnol Lett 34(12):2291–2298 Lopez-Leon T, Carvalho ELS, Seijo B, Ortega-Vinuesa JL, BastosGonzailez D (2005) Physicochemical characterization of chitosan nanoparticles: electrokinetic and stability behavior. J Colloid Interface Sci 283(2):344–351 Ma Y, Liu P, Si C, Liu Z (2010) Chitosan nanoparticles: preparation and application in antibacterial paper. J Macromol Sci Part B 49(5):994–1001

Environ Chem Lett (2018) 16:101–112 Mahdavi B, Rahimi A (2013) Seed priming with chitosan improves the germination and growth performance of ajowan (carum copticum) under salt stress. EurAsia J Biosci 7:69–76 Makhluf S, Dror R, Nitzan Y, Abramovich Y, Jelinek R, Gedanken A (2005) Microwave assisted synthesis of nanocrystalline mgo and its use as a bacteriocide. Adv Funct Mater 15(10):1708–1715 Malmiri HJ, Jahanian MAG, Berenjian A (2012) Potential applications of chitosan nanoparticles as novel support in enzyme immobilization. Am J Biochem Biotechnol 8(4):203–219 Manikandan A, Sathiyabama M (2016) Preparation of chitosan nanoparticles and its effect on detached rice leaves infected with pyricularia grisea. Int J Biol Macromol 84:58–61 Manjusha EM, Mohan JC, Manzoor K, Nair SV, Tamura H, Jayakumar R (2010) Folate conjugated carboxymethyl chitosan–manganese doped zinc sulphide nanoparticles for targeted drug delivery and imaging of cancer cells. Carbohydr Polym 80:414–420 Min B-M, Lee SW, Lim JN, You Y, Lee TS, Kang PH, Park WH (2004) Chitin and chitosan nanofibers: electrospinning of chitin and deacetylation of chitin nanofibers. Polymer 45(21):7137–7142 Mohammadpour Dounighi N, Eskandari R, Avadi M, Zolfagharian H, Mir Mohammad Sadeghi A, Rezayat M (2012) Preparation and in vitro characterization of chitosan nanoparticles containing Mesobuthus eupeus scorpion venom as an antigen delivery system. J Venom Anim Toxins Incl Trop Dis 18(1):44–52 Mondal M, Rana MIK, Dafader N, Haque M (2011) Effect of foliar application of chitosan on growth and yield in Indian spinach. J Agrofor Environ 5(1):99–102 Mondal M, Malek M, Puteh A, Ismail M, Ashrafuzzaman M, Naher L (2012) Effect of foliar application of chitosan on growth and yield in okra. Aust J Crop Sci 6(5):918 Muzzarelli RAAJC, Gooday GW (1986) Chitin in nature and technology. Plenum Publishing Corporation, New York Namasivayam SKR, Roy EA (2013) Enhanced antibiofilm activity of chitosan stabilized chemogenic silver nanoparticles against Escherichia coli. Int J Sci Res 2013:591 Nge KL, Nwe N, Chandrkrachang S, Stevens WF (2006) Chitosan as a growth stimulator in orchid tissue culture. Plant Sci 170(6):1185–1190 Nguyen T, Dzung T, Cuong P (2014) Assessment of antifungal activity of turmeric essential oil-loaded chitosan nanoparticles. J Chem Biol Phys Sci 4:2347–2356 Nguyen TV, Nguyen TTH, Wang S-L, Vo TPK, Nguyen AD (2016) Preparation of chitosan nanoparticles by tpp ionic gelation combined with spray drying, and the antibacterial activity of chitosan nanoparticles and a chitosan nanoparticle–amoxicillin complex. Res Chem Intermed 2016:1–11 Niwa T, Takeuchi H, Hino T, Kunou N, Kawashima Y (1993) Preparations of biodegradable nanospheres of water-soluble and insoluble drugs with d, l-lactide/glycolide copolymer by a novel spontaneous emulsification solvent diffusion method, and the drug release behavior. J Control Release 25(1):89–98 Ohkawa K, Cha D, Kim H, Nishida A, Yamamoto H (2004) Electrospinning of chitosan. Macromol Rapid Commun 25(18):1600–1605 Olivera S, Muralidhara HB, Venkatesh K, Guna VK, Gopalakrishna K, Kumar Y (2016) Potential applications of cellulose and chitosan nanoparticles/composites in wastewater treatment: a review. Carbohydr Polym 153:600–618 Onsosyen E, Skaugrud O (1990) Metal recovery using chitosan. J Chem Technol Biotechnol 49(4):395–404 Ottey MH, Varum KM, Smidsra DO (1996) Compositional heterogeneity of heterogeneously deacetylated chitosans. Carbohydr Polym 29(1):17–24 Panyam J, Labhasetwar V (2003) Biodegradable nanoparticles for drug and gene delivery to cells and tissue. Adv Drug Deliv Rev 55(3):329–347

111 Park JK, Chung MJ, Choi HN, Park YI (2011) Effects of the molecular weight and the degree of deacetylation of chitosan oligosaccharides on antitumor activity. Int J Mol Sci 12(1):266–277 Peppas NA, Huang Y (2004) Nanoscale technology of mucoadhesive interactions. Adv Drug Deliv Rev 56(11):1675–1687 Perera U, Rajapakse N (2013) Chitosan nanoparticles: preparation, characterization, and applications. In: Kim SK (ed) Seafood processing by-products: trends and applications. Springer, New York, pp 371–387 Pilon L, Spricigo PC, Miranda M, Moura MR, Assis OBG, Mattoso LHC, Ferreira MD (2015) Chitosan nanoparticle coatings reduce microbial growth on fresh-cut apples while not affecting quality attributes. Int J Food Sci Technol 50(2):440–448 Plainsirichai M, Leelaphatthanapanich S, Wongsachai N (2014) Effect of chitosan on the quality of rose apples (syzygium agueum alston) cv. Tabtim chan stored at an ambient temperature. APCBEE Procedia 8:317–322 Postma J, Stevens LH, Wiegers GL, Davelaar E, Nijhuis EH (2009) Biological control of pythium aphanidermatum in cucumber with a combined application of lysobacter enzymogenes strain 3.1 T8 and chitosan. Biol Control 48(3):301–309 Puvvada YS, Vankayalapati S, Sukhavasi S (2012) Extraction of chitin from chitosan from exoskeleton of shrimp for application in the pharmaceutical industry. Int Curr Pharm J 1(9):258–263 Qi L, Xu Z, Jiang X, Hu C, Zou X (2004) Preparation and antibacterial activity of chitosan nanoparticles. Carbohydr Res 339(16):2693–2700 Raafat D, Von Bargen K, Haas A, Sahl H-G (2008) Insights into the mode of action of chitosan as an antibacterial compound. Appl Environ Microbiol 74(12):3764–3773 Rajalakshmi A, Krithiga N, Jayachitra A (2013) Antioxidant activity of the chitosan extracted from shrimp exoskeleton. Middle East J Sci Res 16(10):1446–1451 Rajasree R, Rahate K (2013) An overview on various modifications of chitosan and it’s applications. Int J Pharm Sci Res 4(11):4175 Rajendran R, Abirami M, Prabhavathi P, Premasudha P, Kanimozhi B, Manikandan A (2015) Biological treatment of drinking water by chitosan based nanocomposites. Afr J Biotechnol 14(11):930–936 Ravishankar Rai V, Jamuna Bai A (2011) Nanoparticles and their potential application as antimicrobials, science against microbial pathogens: communicating current research and technological advances. In: Méndez-Vilas A (ed), Formatex, Microbiology Series, No. 3, Vol. 1. Spain, pp 197–209 Rekso GT (2008) Development of radiation degraded chitosan as plant growth promoter and its economic evaluation. JAEA CONF 2008-9 Rinaudo M (2006) Chitin and chitosan: properties and applications. Prog Polym Sci 31(7):603–632 Rodriguez A, Ramirez M, Cardenas R, Hernandez A, Velazquez M, Bautista S (2007) Induction of defense response of Oryza sativa L. against Pyricularia grisea (cooke) Sacc. By treating seeds with chitosan and hydrolyzed chitosan. Pestic Biochem Physiol 89(3):206–215 Saavedra GM, Figueroa NE, Poblete LA, Cherian S, Figueroa CR (2016) Effects of preharvest applications of methyl jasmonate and chitosan on postharvest decay, quality and chemical attributes of fragaria chiloensis fruit. Food Chem 190:448–453 Saharan V, Mehrotra A, Khatik R, Rawal P, Sharma S, Pal A (2013) Synthesis of chitosan based nanoparticles and their in vitro evaluation against phytopathogenic fungi. Int J Biol Macromol 62:677–683 Sailaja A, Amareshwar P, Chakravarty P (2011) Different techniques used for the preparation of nanoparticles using natural polymers and their application. Int J Pharm Pharm Sci 3(Suppl 2):45–50

13

112 Salachna P, Zawadzińska A (2014) Effect of chitosan on plant growth, flowering and corms yield of potted freesia. J Ecol Eng 15(3):97–102 Sarwar A, Katas H, Zin NM (2014) Antibacterial effects of chitosan– tripolyphosphate nanoparticles: impact of particle size molecular weight. J Nanopart Res 16(7):2517 Seyedi SM, Anvaripour B, Motavassel M, Jadidi N (2013) Comparative cadmium adsorption from water by nanochitosan and chitosan. Int J Eng Innov Technol 2(9):145–148 Shahidi F, Arachchi JKV, Jeon Y-J (1999) Food applications of chitin and chitosans. Trends Food Sci Technol 10(2):37–51 Sharma S, Sharma S (2013) Synthesis, characterization and determination of encapsulation efficiency of chitosan nanoparticles for terbinafine. Indo Am J Pharm Res 3(12):1564–1567 Shi B, Shen Z, Zhang H, Bi J, Dai S (2011a) Exploring N-imidazolylO-carboxymethyl chitosan for high performance gene delivery. Biomacromol 13(1):146–153 Shi LE, Tang ZX, Yi Y, Chen JS, Xiong WY, Ying GQ (2011b) Immobilization of nuclease p1 on chitosanmicro-spheres. Chem Biochem Eng Q 25(1):83–88 Shiraishi S, Imai T, Otagiri M (1993) Controlled release of indomethacin by chitosan-polyelectrolyte complex: optimization and in vivo/in vitro evaluation. J Control Release 25(3):217–225 Sims DC, Butler PE, Casanova R, Lee BT, Randolph MA, Lee WA, Yaremchuk MJ et al (1996) Injectable cartilage using polyethylene oxide polymer substrates. Plast Reconstr Surg 98(5):843–850 Sivakami M, Gomathi T, Venkatesan J, Jeong H-S, Kim S-K, Sudha P (2013) Preparation and characterization of nano chitosan for treatment wastewaters. Int J Biol Macromol 57:204–212 Sonia T, Sharma CP (2011) Chitosan and its derivatives for drug delivery perspective. Adv Polym Sci 243:23–53 Sudarshan NR, Hoover DG, Knorr D (1992) Antibacterial action of chitosan. Food Biotechnol 6(3):257–272 Sun K, Li Z (2011) Preparations, properties and applications of chitosan based nanofibers fabricated by electrospinning. Express Polym Lett 5(4):342–361 Thanou M, Nihot M, Jansen M, Verhoef JC, Junginger H (2001) MonoN-carboxymethyl chitosan (MCC), a polyampholytic chitosan derivative, enhances the intestinal absorption of low molecular weight heparin across intestinal epithelia in vitro and in vivo. J Pharm Sci 90(1):38–46 Tiyaboonchai W (2003) Chitosan nanoparticles: a promising system for drug delivery. Naresuan Univ J 11(3):51–66 Van Toan N, Hanh TT (2013) Application of chitosan solutions for rice production in vietnam. Afr J Biotechnol 12(4):382–384 Van SN, Minh HD, Anh DN (2013) Study on chitosan nanoparticles on biophysical characteristics and growth of robusta coffee in green house. Biocatal Agric Biotechnol 2(4):289–294 Vauthier CDC, Chauvierre C, Brigger I, Couvreur P (2003) Drug delivery to resistant tumors: the potential of poly(alkyl cyanoacrylate) nanoparticles. J Control Release 93:151–160 Vazquez-Duhalt R, Tinoco R, D’Antonio P, Topoleski LDT, Payne GF (2001) Enzyme conjugation to the polysaccharide chitosan:

13

Environ Chem Lett (2018) 16:101–112 smart biocatalysts and biocatalytic hydrogels. Bioconjug Chem 12(2):301–306 Wang X, Xing B (2007) Importance of structural makeup of biopolymers for organic contaminant sorption. Environ Sci Technol 41(10):3559–3565 Wang M, Chen Y, Zhang R, Wang W, Zhao X, Du Y, Yin H (2015) Effects of chitosan oligosaccharides on the yield components and production quality of different wheat cultivars (triticum aestivum l.) in northwest china. Field Crop Res 172:11–20 Wei D, Sun W, Qian W, Ye Y, Ma X (2009) The synthesis of chitosanbased silver nanoparticles and their antibacterial activity. Carbohydr Res 344(17):2375–2382 Whitesides GM (2003) The’right’size in nanobiotechnology. Nat Biotechnol 21(10):1161–1165 Xie W, Xu P, Liu Q (2001) Antioxidant activity of water-soluble chitosan derivatives. Bioorg Med Chem Lett 11(13):1699–1701 Xing K, Shen X, Zhu X, Ju X, Miao X, Tian J, Qin S et al (2016) Synthesis and in vitro antifungal efficacy of oleoyl-chitosan nanoparticles against plant pathogenic fungi. Int J Biol Macromol 82:830–836 Yacob N, Mahmud M, Talip N, Hashim K, Harun AR, Zaman K, Dahlan H (2013) Degradation of chitosan for rice crops application. Nucl Sci Tech 24(S1):10301–S010301 Yang K, Xu N-S, Su WW (2010) Co-immobilized enzymes in magnetic chitosan beads for improved hydrolysis of macromolecular substrates under a time-varying magnetic field. J Biotechnol 148(2):119–127 Yen MT, Mau JL (2007) Selected physical properties of chitin prepared from shiitake stipes. LWT Food Sci Technol 40(3):558–563 Yen MT, Yang JH, Mau JL (2008) Antioxidant properties of chitosan from crab shells. Carbohydr Polym 74(4):840–844 Yen MT, Yang JH, Mau JL (2009) Physicochemical characterization of chitin and chitosan from crab shells. Carbohydr Polym 75(1):15–21 Yien L, Zin NM, Sarwar A, Katas H (2012) Antifungal activity of chitosan nanoparticles and correlation with their physical properties. Int J Biomater 2012:1–9 Yoshii F, Zhanshan Y, Isobe K, Shinozaki K, Makuuchi K (1999) Electron beam crosslinked PEO and PEO/PVA hydrogels for wound dressing. Radiat Phys Chem 55(2):133–138 Zhang Y, Zhang X, Ding R, Zhang J, Liu J (2011) Determination of the degree of deacetylation of chitosan by potentiometric titration preceded by enzymatic pretreatment. Carbohydr Polym 83(2):813–817 Zhao LM, Shi LE, Zhang ZL, Chen JM, Shi DD, Yang J, Tang ZX (2011) Preparation and application of chitosan nanoparticles and nanofibers. Braz J Chem Eng 28(3):353–362 Zolghadri S, Jalilian AR, Yousefnia H, Bahrami-Samani A, ShirvaniArani S, Mazidi M, Akhlaghi M, Ghannadi-Maragheh M (2010) Production and quality control of 166Ho-Chitosan for therapeutic applications. Iran J Nucl Med 18(2):1–8