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Application of Chitosan and ItsDerivatives in Analytical Chemistry: AMini-ReviewXiaofang Fu a , Huwei Liu b , Yu Liu a & Yi Liu ba Laboratory for Earth Surface Process, College of Urban andEnvironmental Sciences, Peking University , Beijing , 100871 , Chinab The Key Lab of Bioorganic Chemistry and Molecular Engineering,Ministry of Education, Institute of Analytical Chemistry, College ofChemistry and Molecular Engineering, Peking University , Beijing ,100871 , ChinaPublished online: 03 Dec 2013.

To cite this article: Xiaofang Fu , Huwei Liu , Yu Liu & Yi Liu (2013) Application of Chitosan andIts Derivatives in Analytical Chemistry: A Mini-Review, Journal of Carbohydrate Chemistry, 32:8-9,463-474, DOI: 10.1080/07328303.2013.863318

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Journal of Carbohydrate Chemistry, 32:463–474, 2013Copyright C© Taylor & Francis Group, LLCISSN: 0732-8303 print / 1532-2327 onlineDOI: 10.1080/07328303.2013.863318

Application of Chitosan and ItsDerivatives in AnalyticalChemistry: A Mini-Review

Xiaofang Fu,1 Huwei Liu,2 Yu Liu,1 and Yi Liu2

1Laboratory for Earth Surface Process, College of Urban and Environmental Sciences,Peking University, Beijing 100871, China2The Key Lab of Bioorganic Chemistry and Molecular Engineering, Ministry ofEducation, Institute of Analytical Chemistry, College of Chemistry and MolecularEngineering, Peking University, Beijing 100871, China

Recent progress in the application of chitosan and its derivatives in analytical chem-istry, especially their application in the field of separation science including as capillarycoating materials, chromatographic column fillings, and adsorption materials, duringthe past 8 years is reviewed.

Keywords Analytical chemistry; Application; Chitosan

INTRODUCTION

Chitosan is the randomly deacetylated derivative of chitin that is the second-most abundant natural polysaccharide after cellulose and is abundantly avail-able in marine crustaceans. It is composed of linear β-(1→4)–linked glu-cosamine and N-acetyl glucosamine (Fig. 1a). Chitosan does not elicit adversereactions when in contact with human cells, thus showing inherent biodegrad-ability, good biocompatibility, and specificity to bringing drugs to the targetcell because it is recognizable by the tumor cell. These properties have at-tracted scientific attention to chitin and chitosan.[1] However, the poor solu-bility of chitosan in water and in common organic solvents has so far limitedits widespread application. By utilizing chitosan’s amino and hydroxyl groupsas modification sites, many chitosan derivatives have been obtained via sub-stitution, chain elongation, and depolymerization.[2] These modified chitosanderivatives may have improved solubility in organic solvents and water and

Received September 4, 2013; accepted October 24, 2013.Address correspondence to Xiaofang Fu, Laboratory for Earth Surface Process, Col-lege of Urban and Environmental Sciences, Peking University, Beijing, 100871, China.E-mail: fxiaof@pku.edu.cn

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(a)

(b)

H

H O

OH

HNH2

H

HO

H

OO

HO

HHH

HO

H OH

NH

C O

CH3

n1 n2

H

H O

OCH2COOH

HNH2

H

HO

H

OO

H O

HHH

HO

H OH

NH

C O

CH3

m1 m2

Figure 1: Chemical structures of chitosan (a) and CMC (b).

other useful properties; thus, the application scope of chitosan and its deriva-tives has been significantly extended.

Many free amino and hydroxyl groups are present in chitosan, which hasmade it easy for it to be cross-linked though covalent or ionic bonds. Moreover,the amino groups could be protonated under acidic conditions, making themable to easily adsorb heavy metal ions or react with other groups as well. Be-cause of these special properties, chitosan and its derivatives have been widelyused in various fields. There are a number of reviews about their applicationsin pharmaceuticals, food and nutrition science, agriculture, and environmen-tal protection.[1–4] Recently, there has been much progress in their applicationin analytical chemistry, such as preconcentration of scarce contents, biosensordevelopment, electroanalytical chemistry, and separation materials in chro-matography. In 2006, Li et al.[5] reviewed the progress of the application ofchitosan and its derivatives in analytical chemistry. The purpose of this re-view is to survey the development, since 2006, in the application of chitosanand its derivatives in analytical chemistry, especially in the fields of separationscience.

AS COATING MATERIALS FOR CAPILLARY ELECTROPHORESIS

Capillary electrophoresis (CE) is a useful tool for the analysis of biopolymers,but there is always significant peak tailing or irreversible adsorption in proteinanalysis. To address this issue, variable coating materials have been developed

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Mini-review of Chitosan and Its Derivatives 465

Figure 2: Various schemes of capillary with or without chitosan coating. (a) Uncoatedcapillary with activated silanol groups. (b) Capillary coated with one layer of chitosan orcarboxymethyl chitosan coating.[9,11] (c) Coupled chitosan-modified capillary.[10]

to overcome the adsorption between objective samples and the inner wall ofthe fused silica capillary.[6] Chitosan, which can be adsorbed by the fused silicacapillary at low pH, had been used as a capillary coating material under acidicconditions for inorganic anion, basic drug, and protein analysis by CE.[7–9] Al-though better separation effects could be obtained for the above-mentionedanalysis, the chitosan-coated capillary still had some problems, such as poorstability and narrow pH range. Huang et al.[10] developed a new capillary coat-ing material by coupling chitosan to glutaraldehyde, with which high-efficiencyanalysis of some acidic and basic proteins could be realized. To achieve stabil-ity and repeatability with a coupled chitosan-modified capillary, three coatinglayers were necessary. The different schemes of capillary with or without chi-tosan coating are shown in Figure 2. Carboxymethyl chitosan (CMC, Fig. 1b)was shown to have better solubility than that of chitosan in water. Thus, itwas directly dissolved in water and used as a coating material to modify theinner wall of capillary for basic protein and recombinant human erythropoi-etin (rhEPO) analysis in our work.[11] It was proved as an excellent and cost-effective capillary coating material with high endurance, good chemical stabil-ity, and wide pH compatibility range. Because of its stability, the CMC coatingcould be applied to capillary electrophoresis-mass chromatography (CE-MS),which was employed to determine a toxic component in traditional Chinesemedicine.[12] Furthermore, dynamic CMC coating was developed to separate

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proteins, aristolochic acids, and inorganic anions in our lab, with which highsensitivity for the detection of α-lactalbumin was achieved.[13,14] Besides beingused as coating materials, chitosan has also been employed as additives foronline electrophoresis enrichment, by which four organic acid constituents ofPlateau alfalfa roots were determined, in which study 3×102 to 1.5×104 foldsof enrichment were achieved.[15] The above-mentioned studies clearly indicatethat chitosan and its derivatives have high potential as coating materials andadditives for CE and CE-MS analysis of biomolecules, inorganic anions, andother compounds.

AS STATIONARY MATERIALS FOR CHROMATOGRAPHIC COLUMNS

In the past decades, chitosan and its derivatives have been widely used as mod-ified materials of the stationary phase for chromatographic columns. Throughreacting with the free amino groups of chitosan, glutaraldehyde-modified chi-tosan was developed as a hydrophobic interaction chromatography (HIC) ma-trix for the analysis of enzymes. It was proved to be an excellent adsor-bent because of its chemical stability and biocompatibility.[16,17] In addition,n-valeraldehyde-modified cross-linked chitosan was prepared as an HIC ma-trix, through which α-amylase could be purified successfully with satisfactoryrecovery.[18]

Affinity chromatography is an excellent technique for the purification ofproteins, since it can preserve the biological activity of proteins. Chitosanbeads as affinity adsorbent carrier were prepared via reaction with glutaralde-hyde, which has attracted considerable attention for protein purification.[19–21]

Moreover, chitosan could also be utilized to coat ceramic support to form a hy-brid chitosan/ceramic membrane, which has also been used as a support inaffinity membrane chromatography for protein purification.[22,23]

Another important application of chitosan and its derivatives is tothe challenging chiral separation. Chitosan and its derivatives as chi-ral selectors were immobilized on allyl silica gel to separate racemiccompounds in high-performance liquid chromatography (HPLC).[24,25] Chi-ral HPLC columns employed to separate racemic compounds[26–28] havebeen fabricated with several chitosan derivatives, including phenylcarba-mate, N-nicotinoyl-L-phenylalaninate and 3,5-dimethylphenylisocyanate, andtris(3-chlorophenylcarbamate) of chitosan. In addition, chitosan and itsderivatives have also been utilized as chiral stationary phase for open-tubular capillary electrochromatography (OT-CEC) in recent years. Newnanomaterials were prepared for chiral separation through copolymeriza-tion of chitosan (CS) with methacrylamide (MAA), and the MAA-CS mod-ified capillary was utilized to well separate tryptophan enantiomers.[29]

3-Glycidyloxypropyltrimethoxysilane-modified and SiH-modified cross-linkedchitosan capillaries were also prepared and successfully used to separate the

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racemate of ibuprofen.[30] Moreover, columns of a sol-gel coated with chitosan-graft-(β-cyclodextrin) were prepared and have shown better separation of iso-meric xanthopterin.[31] Chen[32] compared the properties and the separate ca-pacity of three open-tubular sol-gel capillary columns coated with chitosan andfound that the enantiomers of phenylglycine, alanine, tryptophan, and cate-chin could be separated with different resolutions. Chitosan as a chiral reagentis of low cost, wide choice, and excellent selectivity, and moreover, it can beeasily converted to different derivatives to serve as the coating and stationaryphase of HPLC and electrophoresis to separate various compounds accordingto their structural features.

APPLICATION IN CONCENTRATION AND EXTRACTION

Heavy metal ions found in natural water, air, and food products at trace lev-els can bring harmful effects to human, animals, and plants. On the otherhand, some metal ions have been recognized as essential trace elements formany species, including human beings. Therefore, monitoring and analyz-ing these metals is very important. Because they always present in complexmatrices and in trace amounts, many of the analytical techniques, such asinductively coupled plasma-atomic emission spectrometry (ICP-AES), atomicabsorption spectrometry (AAS), and inductively coupled plasma-mass spec-trometry (ICP-MS), do not have enough sensitivity and cannot be directly used.Therefore, preconcentration or separation of samples from matrices is a nec-essary step before analysis. Solid-phase extraction techniques using chelat-ing resins are useful for this purpose. As chitosan can form stable chelatingcompounds with many transition metal ions through its amino and hydroxylgroups, it has been used to concentrate various metal ions via selective ad-sorption. Moreover, cross-linked chitosan and chitosan derivatives have beenprepared to further improve chitosan’s chemical durability and selectivity ofspecific metal ions. Modified chitosan resins that have been synthesized forthe concentration of ions include chitosan derivatives of histidine,[33] tris(2-aminoethyl)amine,[34] serine diacetic acid,[35] threonine,[36] 2-amino-5-hydroxybenzoic acid,[37] 3-nitro-4-amino benzoic acid,[38] 2-aminopyridine-3-carboxylicacid,[39] and di-2-propanolamine.[40] These chitosan resins have been exploredfor concentrating the ions of Ag, As, Be, Cd, Co, Cu, Ga, In, Ni, Pb, Sc, Th,U, V, Hg, Mo, Zn, Ge, and some rare earth elements at trace levels in en-vironmental samples. Table 1 shows the structures of these chitosan resinsand the elements that they could selectively absorb. Besides these metal ele-ments, octadecyl-functionalized chitosan-coated magnetite nanoparticles wereused as the adsorbent to extract trace amounts of pollutants from environmen-tal water samples. In this method, perfluorinated compounds were trapped bythe octadecyl group, and the positively charged chitosan polymer coating could

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Table 1: Structures of the chitosan resins with different functionalization

Structure of Binding Structure of Bindingmodified chitosan elements modified chitosan elements

CCTS-histidine[33] Ag CCTS-TAA[34] Hg

CCTS-SDA[35] Cd, Pb, V, Cu,Ni, Sc, Dy, Er, Eu,Lu, Yb, Gd, Ho

CCTS-Thr[36] Mo, V, Cu

CCTS-AHBA[37] Ag, Be, Cd, Co,Cu, Ni, Pb, U,V, and rare earthelements

CCTS-NABA[38] Mo

(continued on next page)

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Table 1: Structures of the chitosan resins with different functionalization (continued)

Structure of Binding Structure of Bindingmodified chitosan elements modified chitosan elements

CCTS-ACA[39] Cd(II), Zn(II) CCTS-DPA[40] Ge

CCTS: cross-linked chitosan; ACA: 2-aminopyridine-3-carboxylic acid; AHBA: 2-amino-5-hydroxybenzoic acid; DPA: di-2-propanolamine; NABA: 3-nitro-4-amino benzoic acid; SDA: serine di-acetic acid; TAA: tris(2-aminoethyl)amine; Thr: threonine; cross-linker: -CH2-CH(OH)-CH2-O-CH2-CH2-O-CH2-CH(OH)-CH2-.

also enrich the perfluorinate compounds.[41] As mentioned above, chitosan andits derivatives have been proved to be extremely promising materials for theconcentration and extraction of metal ions from complex matrices, and therestill should be many potential resins that can be developed for the analysis ofspecific metals in the future.

APPLICATION IN ELECTROANALYTICAL CHEMISTRY AND BIOSENSORDEVELOPMENT

Electrochemical methods can be widely useful for chemical detection as theyare fast and simple, but their selectivity is always an issue. Therefore, theselectivity of an electrode in terms of its reaction or adsorption is the key toimprove the selection of electrochemical detection. Chitosan and its deriva-tives had excellent chelating and adsorbed properties due to chitosan’s reactiveamino and hydroxyl groups, which could be used to prepare chemical-modifiedelectrodes. The electrochemical behavior of precious metal elements, such asAu, Ag, Pt, and Pd, on the glassy carbon electrode modified with chitosan andtheir applications were reported. Experimental results indicated that thesemetal ions could be enriched selectively and produce sensitive anodic strippingpeak current.[42] Payne and coworkers[43] employed chitosan-coated electrodes

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to enhance the discriminating power for the electrochemical analysis of an-tioxidant phenols in foods. Recently, a film of nanodiamond-graphite/chitosanwas used to modify a novel glassy carbon electrode for azathioprine determi-nation. The modified electrode could be easily prepared and had high stability,sensitivity, catalytic activity, and reproducibility.[44]

Chitosan applied to biosensors has been developing rapidly because ofits many special properties, such as biocompatibility, high permeability forwater, good film-forming ability, and nontoxicity. It had been utilized as anexcellent matrix for enzyme immobilization.[45] A graphene oxide-chitosannanocomposite-based electrochemical DNA biosensor has been recently devel-oped for diagnosis of typhoid.[46] Suginta et al.[47] reviewed this application ofchitosan in electrochemical sensors. Many enzyme biosensors were fabricatedby using multiwalled carbon nanotube (MWNT)/chitosan-modified glass car-bon electrode.[48,49] Self-assembling gold nanoparticales on chitosan hydrogel-modified Au electrodes were also prepared for immobilization of horseradishperoxidase.[50] ds-DNA-decorated chitosan-modified MWNTs were also used asbiosensors for voltammetric detection of herbicide amitrole. Despite the ad-vantages of chitosan used in biosensors, the poor solubility of chitosan mightlimit its application. This problem could be addressed by functionalization ofchitosan with quaternary ammonium salt to result in cationic chitosan. O-(2-hydroxyl) propyl-3-trimethylammonium chitosan chloride (O-HTCC) nanopar-ticles developed by Sun and Wan[51] have been used to immobilize an enzymefor glucose biosensors.[52] From these publications, it is clear that nanomateri-als of chitosan and its derivatives have a promising future for the developmentof modified electrodes and biosensors.

CONCLUSION

Chitosan and its derivatives have been used widely in analytical chemistry,and they have been proved as effective coatings for fused capillary, modifyingreagents for electrodes and chromatographic columns, enzyme-immobilizingmatrices, and adsorption materials for sample concentration. Due to the exis-tence of free amino and hydroxyl groups in chitosan, many of its derivativeswith unique properties could be developed for various applications. For exam-ple, carboxymethyl-chitosan was used as a new and effective capillary coatingfor CE analysis of glycoproteins, basic proteins, inorganic ions, and componentsin Chinese herbal medicine. β-Cyclodextrin-grafted chitosan have been pre-pared[53] and used as capillary coating for the separation of chiral compoundsand other compounds using CE and CE-MS. Many metal ions were concen-trated, and various racemic mixtures have been separated by using differentchitosan derivatives. Nowadays, the study of chitosan derivatives used as chi-ral separation reagents, enzyme-immobilizing matrices, electrode-modifying

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reagents, and adsorption materials has attracted growing attention for theirnontoxicity, biocompatibility, and cost-effectiveness. Therefore, it is foresee-able that more and more chitosan derivatives will be prepared and investi-gated in the future, and their application in analytical chemistry will becomewidespread and significant.

FUNDINGFunding for this study was provided by the National Natural Science Foun-

dation of China (41101490).

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