Accepted Manuscript

Title: Application of carbon-based nanomaterials in samplepreparation: A review

Author: <ce:author id="aut0005" biographyid="vt0005">Bo-Tao Zhang<ce:author id="aut0010"biographyid="vt0010"> Xiaoxia Zheng<ce:authorid="aut0015" biographyid="vt0015"> Hai-Fang Li<ce:authorid="aut0020" biographyid="vt0020"> Jin-Ming Lin

PII: S0003-2670(13)00428-5DOI: http://dx.doi.org/doi:10.1016/j.aca.2013.03.054Reference: ACA 232483

To appear in: Analytica Chimica Acta

Received date: 25-1-2013Revised date: 14-3-2013Accepted date: 22-3-2013

Please cite this article as: B.-T. Zhang, X. Zheng, H.-F. Li, J.-M. Lin, Application ofcarbon-based nanomaterials in sample preparation: A review, Analytica Chimica Acta(2013), http://dx.doi.org/10.1016/j.aca.2013.03.054

This is a PDF file of an unedited manuscript that has been accepted for publication.As a service to our customers we are providing this early version of the manuscript.The manuscript will undergo copyediting, typesetting, and review of the resulting proofbefore it is published in its final form. Please note that during the production processerrors may be discovered which could affect the content, and all legal disclaimers thatapply to the journal pertain.

Page 1 of 63

Accep

ted

Man

uscr

ipt

Graphical Abstract

Carbon-based nanomaterials in sample preparation

*Graphical Abstract

Page 2 of 63

Accep

ted

Man

uscr

ipt

Highlights

A review on carbon-based nanomaterials’ applications in sample preparation.

Particular attention is paid to graphene for its growing papers recently.

Research status and perspective of them are also discussed.

*Highlights

Page 3 of 63

Accep

ted

Man

uscr

ipt

1

Application of carbon-based nanomaterials in sample preparation: A 1

review 2

Bo-Tao Zhanga, Xiaoxia Zhenga,b, Hai-Fang Lib, Jin-Ming Linb* 3

a College of Water Sciences, Beijing Normal University, Beijing 100875, China 4 b Beijing Key Laboratory of Microanalytical Methods and Instrumentation, 5

Department of Chemistry, Tsinghua University, Beijing 100084, China 6

7

Abstract 8

In this paper, a broad overview on the applications of different carbon-based 9

nanomaterials, including nanodiamonds, fullerenes, carbon nanotubes, graphene, 10

carbon nanofibers, carbon nanocones-disks and nanohorns, as well as their 11

functionalized forms, in sample preparation is provided. Particular attention has been 12

paid to graphene because many papers regarding its application in this research field 13

are becoming available. The distinctive properties, derivatization methods and 14

application techniques of these materials were summarized and compared. According 15

to their research status and perspective, these nanomaterials were classified to four 16

groups and characteristics and future trends of every group were discussed. 17

18

Keywords: Carbon-based nanomaterials; Sample preparation; Review; Graphene. 19

20

* Tel/Fax: +86-10-62792343, E-mail: jmlin@mail.tsinghua.edu.cn (J.-M. Lin).

Page 4 of 63

Accep

ted

Man

uscr

ipt

2

Abbreviations: APTES, 3-aminopropyltriethoxysilane; BTEX, benzene, toluene, 1

ethylbenzene, and o-xylene; CNFs, carbon nanofibers; CNTs, carbon nanotubes; 2

DAD, diode array detection; DCC, N,N’-dicyclohexylcarbodiimide; DMF, 3

dimethylformamide; DVB, divinylbenzene; ECD, electron capture detector; EDC, 4

N-(3-dimethylaminopropyl)-N-ethylcarbodiimide hydrochloride; EF, enrichment 5

factor; ESI, electrospray ionization; FAAS, flame atomic absorption spectrometry; 6

FID, flame ionic detector; FL, fluorescence spectrophotometer; G, graphene; GC, gas 7

chromatography; GCE, glassy carbon electrode; HPLC, high performance liquid 8

chromatography; ICP, inductively coupled plasma; IT, ion trap; LLE, liquid-liquid 9

extraction; LOD, limit of detection; MALDI, matrix-assisted laser 10

desorption/ionization; MIPs, molecularly imprinted polymers; MS, mass spectrometry; 11

MSPD, matrix solid-phase dispersion; MSPE, magnetic solid-phase extraction; 12

MWCNTs, multi-walled carbon nanotubes; NaDDC, sodium diethyldithiocarbamate; 13

NHS, N-hydroxysuccinimide; NP, normal-phase; PAAm, polyallylamine; PAHs, 14

polycyclic aromatic hydrocarbons; PBDEs, polybrominated diphenyl ethers; PCBs, 15

polychlorinated biphenyls; PDMS, polydimethylsiloxane; PEG, poly(ethylene glycol); 16

PMME, polymer monolith microextraction; PVA, poly(vinyl alcohol); RP, 17

reversed-phase; SDS-PAGE, sodium dodecyl sulfate polyacrylamide gel 18

electrophoresis assay; SELDI, surface enhanced laser desorption ionization; SEM, 19

scanning electron microscope; SFE, supercritical fluid extraction; SPE, solid-phase 20

extraction; SPME, solid-phase microextraction; SRSE, stir rod sorptive extraction; 21

SWCNTs, single-walled carbon nanotubes; SWNHs, single-walled carbon nanohorns; 22

TCM, traditional Chinese medicine; TOF, time of flight; UV, ultraviolet; YCC, yeast 23

cytochrome c; μ-SPE, micro-solid-phase extraction. 24

25

Page 5 of 63

Accep

ted

Man

uscr

ipt

3

1. Introduction 1

An analytical process usually has several steps, such as sampling, sample 2

preparation, separation, detection, data handling and treatment, to offer the required 3

results. Of these steps, sample preparation might be the most important when target 4

analytes are in complex matrices or direct analysis is not practical due to the lack of 5

selectivity and sensitivity. Numerous potential interferents and low concentrations of 6

analytes make a previous extraction procedure, which usually involves isolation and 7

enrichment of the analytes, necessary. The development of new extraction techniques 8

and improvement of existing techniques using novel extraction materials are the main 9

trends in this research area. Regarding the latter issue, nanomaterials are promising 10

tools [1]. 11

Nanomaterials are those particles that present at least one dimension in the 12

nanometer range giving them novel and special properties. The main advantages of 13

these materials are a high surface-to-volume ratio, easy derivatization procedures, and 14

unique thermal, mechanical or electronic properties. Carbon-based nanomaterials, the 15

important parts of these materials, have fascinated the scientific community since 16

their discovery. In recent years, a large number of carbon-based nanoparticles have 17

been investigated as sorbent material in sample preparation, including nanodiamonds, 18

fullerenes, carbon nanotubes, graphene, carbon nanofibers, carbon nanocones-disks 19

and nanohorns, as well as their functionalized forms. The characteristic structures of 20

carbon-based nanomaterials allow them to interact with organic molecules via 21

non-covalent forces, such as hydrogen bonding, π-π stacking, electrostatic forces, van 22

Page 6 of 63

Accep

ted

Man

uscr

ipt

4

der Waals forces and hydrophobic interactions. These interactions and their hollow or 1

layered, nanosized structures make them good candidates for use as adsorbents [2]. 2

Considering the aforementioned properties, carbon-based nanomaterials have found 3

a wide range of applications in different sample preparation technologies. This review 4

paper intends to provide a broad snapshot of the applications of different 5

carbon-based nanomaterials in sample preparation. Particular attention has been paid 6

to graphene because many papers regarding its application in this research area have 7

become available since the first paper was published in 2010. 8

9

2. Graphene 10

Since the first experimental evidence of the electronic properties of graphene in 11

2004, recent years have witnessed many breakthroughs in research on it [3, 4]. 12

Graphene, which is considered the basic building block of all graphitic forms 13

(including carbon nanotubes (CNTs), graphite and fullerene), possesses a single layer 14

of carbon atoms in a closely packed honeycomb two-dimensional lattice. Graphene 15

has a large specific surface area (theoretical value 2630 m2 g-1)[5], and both sides of 16

its planar sheets are available for molecule adsorption. Furthermore, the large 17

delocalized π-electron system of graphene can form strong π-stacking interaction with 18

the benzene ring, which might make graphene a good choice for the extraction of 19

benzenoid form compounds. Finally, graphene can be easily modified with functional 20

groups, especially via graphene oxide. The exceptional properties of graphene make it 21

a superior candidate as a good adsorbent in different sample preparation methods. 22

Page 7 of 63

Accep

ted

Man

uscr

ipt

5

Table 1 compiles the most recent of these applications. 1

2

2.1 Solid-phase extraction with graphene 3

Solid-phase extraction (SPE) is a popular sample preparation technique because of 4

its simplicity, rapidity, minimal cost, low consumption of reagents, and ability to 5

combine with different detection techniques whether in on-line or off-line mode [6, 7]. 6

The sorbent material used, which is the core of SPE, determines the selectivity and 7

efficiency of the method. 8

Graphene was used as SPE sorbents by packing into a commercial cartridge to 9

extract chlorophenols and heavy metals (Pb or Cr with different chelating reagents) in 10

water samples [5, 8, 9], glutathione in human plasma and neurotransmitters from rat 11

brain [10, 11]. Its performance was evaluated by comparing with several commonly 12

used reserved-phase sorbent materials, including C18 silica, graphitic carbon, CNTs 13

under same or optimum conditions. Graphene yielded the best recoveries of these 14

sorbent materials and it surpassed CNTs by having both sides of its planar sheet and 15

remaining hydrophilic groups. Furthermore, it can be reused for up to 50 16

adsorption-elution cycles with acceptable recoveries for the chlorophenols’ and heavy 17

metal pre-concentration. 18

Miniscule graphene might escape from the cartridge and aggregation of graphene 19

could occur when graphene or its oxide was directly used as SPE sorbent [12]. To 20

avoid these problems, graphene oxide was linked to the amino groups of an 21

amino-terminated silica adsorbent in organic phase. Polar graphene oxide@silica 22

Page 8 of 63

Accep

ted

Man

uscr

ipt

6

could be used as normal-phase SPE for hydroxylated polybrominated diphenyl ethers 1

and graphene@silica, which was obtained by hydrazine reduction as illustrated in Fig. 2

1., could be used as reversed-phase for chlorophenols or peptides. Their performances 3

were superior or comparable to commercially available adsorbents [13]. 4

TiO2-graphene was also prepared by hydrothermal method to effectively avoid 5

aggregation of graphene when it was used in a cartridge [14]. 6

7

2.2 Magnetic solid-phase extraction with graphene 8

Graphene can be modified with magnetic particles as magnetic solid-phase 9

extraction (MSPE). In an MSPE process, short equilibrium time is required due to a 10

fast mass transfer and the analyte-loaded sorbent can be easily separated via an 11

external magnetic field [15, 16]. The group of Wang synthesized magnetic graphene 12

nanoparticles by in situ chemical coprecipitation of Fe2+ and Fe3+ in an alkaline 13

solution in the presence of graphene and applied them in extracting a series of 14

pollutants, such as phthalate esters [17], triazine herbicides [18], carbamate pesticides 15

[19], triazole fungicides [20] and neonicotinoid insecticides [21] from liquid samples 16

with enrichment factors from 247 to 5824. The Fe3O4 nanoparticles were well 17

distributed on graphene sheets and this material, with saturation magnetization 18

intensity of 72.8 emu g-1 and specific surface area of 225 m2 g-1, can be reused more 19

than ten times without a significant decrease in the extraction capability. The activated 20

graphene, treated by HNO3, could easily combine with Fe3O4 spheres via a simple 21

hydrothermal reaction with polyethylene glycol as the capping agent and trisodium 22

Page 9 of 63

Accep

ted

Man

uscr

ipt

7

citrate as a modification [22]. The magnetic graphene served as an adsorbent in 1

simplified sample pretreatment and a matrix in MALDI MS, which eliminated the 2

interferences caused by conventional organic matrices. 3

In order to protect Fe3O4 spheres from corrosion, oxidation and agglomeration, the 4

particles were synthesized using a solvothermal method, followed by coating with 5

silica through a sol-gel process to obtain Fe3O4@SiO2 microspheres. Luo et al. [23] 6

immobilized graphene sheets onto silica-coated magnetic microspheres by simple 7

adsorption and used as an extraction media for the enrichment of trace amount of six 8

sulfonamide antibiotics in environmental water samples. Liu et al. [24] further 9

functionalized Fe3O4@SiO2 microspheres with 3-aminopropyltriethoxysilane (APTES) 10

to make the particles positively charged. Graphene oxide was assembled on the 11

amino-functional silica-coated Fe3O4 spheres through electrostatic interactions. 12

Finally, the graphene oxide sheets on the particle surface were reduced to graphene 13

with hydrazine. This material showed excellent performance in enhancement of 14

MALDI-TOF MS signals of proteins and peptides in highly saline solutions. The 15

enrichment process was facile and quick, and there was no deterioration in analytical 16

performance during the seven successive extractions for protein enrichment. 17

There also exist other ways to use magnetic graphene in sample pretreatment. 18

Graphene is not an ideal adsorbent for ionized compounds, but it might change when 19

magnetic graphene was used as the support for cationic or anionic hemimicelles and 20

admicelles. It exhibited higher loading capacity than conventional materials and pure 21

Fe3O4 nanoparticles, and was successfully applied to extract different types of 22

Page 10 of 63

Accep

ted

Man

uscr

ipt

8

analytes including perfluoroalkyl substances, alkylphenols and 1

alkyltrimethylammonium salts from environmental water samples [25]. Magnetic 2

graphene and CNT composites were synthesized via a simple solvothermal synthesis 3

of magnetite particles in the presence of acid treated CNTs and graphene. Compared 4

with magnetic graphene, magnetic CNTs and a mixture of magnetic graphene and 5

magnetic CNTs, magnetic graphene/CNT composites have several advantages such as 6

higher efficiency, a facile desorption/ionization process and higher peak intensities for 7

analytes using MALDI-TOF MS because the combination of graphene and CNTs 8

make the matrix more thermally and electrically conducting in which electrons shoot 9

along with minimal resistance [26]. 10

11

2.3 Solid-phase microextraction with graphene 12

The solid-phase microextraction (SPME) technique is a solvent-free and 13

miniaturized microextraction technique which integrates sampling, extraction, 14

preconcentration and sample introduction in a single step [27, 28]. It is based on the 15

distribution equilibrium of analytes between the matrix and a fiber coated with a 16

stationary phase, so the fiber coating material is critical in improving the SPME 17

performance. Graphene was immobilized on the SPME fiber by different 18

non-covalent or covalent methods, most of which exhibited better extraction 19

efficiency, higher mechanical and thermal stability, and longer life span than 20

commercial materials in SPME. The group of Chen first prepared graphene-coated 21

SPME fiber by repeatedly immersing a clean stainless steel wire into graphene 22

Page 11 of 63

Accep

ted

Man

uscr

ipt

9

suspension and drying it in air to obtain 6-8 μm coating. Its extraction efficiency is 1

approximate 1.5-fold higher than commercial 100 μm polydimethylsiloxane (PDMS) 2

or 65 μm PDMS/divinylbenzene (PDMS/DVB) coating fibers. No obvious extraction 3

efficiency change after 250 extractions, thermal or different solvent treatments was 4

observed [29]. The group of Wang used the similar methods to prepare 5

graphene-coated SPME fiber for determination of carbamate pesticides and triazine 6

herbicides in water samples [30, 31]. 7

Graphene was also immobilized on SPME fiber by other non-covalent methods. 8

Microwave synthesized graphene was immobilized on a stainless steel fiber using 9

silicone glue as a binder to get average 50 μm coating. The performance and 10

feasibility of this fiber was evaluated under one-step microwave assisted headspace 11

SPME and this fiber showed high extraction efficiency and a long life span (over 250 12

times) [32]. A polypyrrole/graphene-coated fiber was prepared by electrochemically 13

polymerizing pyrrole and graphene on a stainless steel fiber by group of Chen [33]. 14

The extraction efficiency of the polypyrrole/graphene-coated fiber was obviously 15

higher than that of the polypyrrole/graphene oxide-coated fiber since graphene has a 16

larger delocalized π-electron system. The fiber could be used more than 50 times 17

without obvious decrease in extraction ability and no measurable change in different 18

organic solvents. Zhang and Lee [34, 35] used the sol-gel approach to coat graphene 19

on a stainless steel plunger which was etched by HF with a rough and porous surface. 20

The thickness of the sol-gel film was controlled by the duration of coating and the 21

etching, and final thickness was approximate 8 μm. The sol-gel graphene fiber’s 22

Page 12 of 63

Accep

ted

Man

uscr

ipt

10

thermal stability was validated by results of 340 ◦C thermal treatment and 1

thermogravimetric analysis. The enrichment factors for ultraviolet filters or 2

polybrominated diphenyl ethers were high and ranged from 1080 to 10155. Since the 3

strong affinity of ZnO to sulfur-containing groups, graphene-supported zinc oxide was 4

immobilized on a silica fiber by the sol-gel approach [36]. The fiber showed a much 5

higher adsorption affinity toward sulfur compounds than other compounds without 6

sulfur-containing groups and was used to extract sulfur volatiles in Allium species. 7

High mechanical and thermal stability of the fiber coating allowed it to have a long 8

lifespan of more than 200 replicate extractions. 9

In order to improve the chemical stability, APTES was used as a crossing agent to 10

covalently bond graphene oxide with hydroxylated silica fiber. The graphene 11

oxide-bond SPME fiber exhibited excellent extraction efficiency for PAHs and good 12

stability towards organic solvents, acidic and alkali solutions or high temperature [37]. 13

It can also be deoxidized by hydrazine to give the graphene-coated SPME fiber which 14

is demonstrated in Fig. 2. The chemical bonding allowed the graphene-bond fiber 15

more than 150 replicate extractions without measurable loss of performance. This 16

fiber exhibited higher enrichment factors (EFs, 6354-71872) from 2-fold for 17

naphthalene to 17-fold for benzo(b)fluoranthene as compared to the commercial 18

PDMS fiber, and the EFs increased with the number of condensed rings of PAHs. 19

According to the results of selectivity study for PAHs, aromatic compounds with 20

different substituent groups and some aliphatic hydrocarbons, the strong adsorption 21

affinity was attributed to the strong π-π stacking, π-π electron-donor-acceptor 22

Page 13 of 63

Accep

ted

Man

uscr

ipt

11

interaction, and hydrophobic interaction between the compounds and graphene 1

surface [38]. 2

3

2.4 Graphene as an extractor and matrix substrate in LDI MS 4

Graphene can serve as a matrix substrate for LDI MS analysis for its efficient 5

ionization/desorption (UV absorption at 250-350 nm and excellent electrical- and 6

thermal-conductivity), high salt-tolerance and good reproducibility. After extraction, 7

the analyte-loaded sorbent can subject to MS analysis with no elution step, in which 8

graphene can be used as both extractor and matrix substrate to greatly improve the 9

detection limit [39, 40]. The group of Zhang utilized both graphene and graphene 10

oxide to enrich and ionize different compounds. Graphene was more effective than 11

graphene oxide for analysis of small molecular components from traditional Chinese 12

medicine herbs [41], while the performance of graphene oxide was better in detecting 13

of long-chain fatty acids and tetracyclines [42, 43]. Tang et al. found graphene had 14

distinct advantages over graphene oxide in terms of its optical absorption and 15

suppression of fragmentation in surface-enhanced laser desorption/ionization 16

(SELDI)-MS, a derivative mode of MALDI [44]. They also used a solution 17

dispersible graphene-titania platform for the selective extraction of phosphopeptides 18

from peptide mixtures or cancer cells. The efficient charge and energy exchange 19

between graphene and TiO2 during laser irradiation in SELDI-TOF MS promoted the 20

soft ionization of analytes and afforded the detection limit in the attomole range [45]. 21

Gulbakan et al. immobilized cocaine and adenosine aptamers onto graphene oxide 22

Page 14 of 63

Accep

ted

Man

uscr

ipt

12

with a bifunctional poly(ethylene glycol) (PEG) molecule (NH2-PEG-SH) linker. This 1

aptamer-conjugated graphene oxide can selectively enrich cocaine or adenosine from 2

plasma samples and direct mass spectrometric readouts can be obtained with greatly 3

improved signal-to-noise ratios [46]. 4

5

2.5 Graphene in other sample preparation techniques 6

There also exist other sample pretreatment techniques with graphene. The 7

sulfonated graphene was enclosed within a polypropylene membrane sheet envelope 8

(1.0 cm × 0.8 cm) for micro-solid-phase extraction (μ-SPE) of PAHs in water samples. 9

The introduction of p-phenyl-SO3H groups into graphene oxide improved the 10

solubility of graphene in water and the electrostatic repulsion by -SO3- group 11

prevented any aggregation. The higher sulfonation degree could lead to an increased 12

surface area available for adsorption resulting in better extraction efficiency [47]. 13

Tong et al. developed monolithic capillary columns with embedded graphene for 14

polymer monolith microextraction (PMME) and enrichment of glucocorticoids. The 15

column was prepared inside fused silica capillaries (320 μm, i.d.) to embed 16

polyvinylpyrrolidone-protected graphene using thermally initiated free-radical 17

polymerization with butyl methacrylate as monomer, ethylene dimethacrylate as a 18

cross-linker, and 1,4-butanediol and 1-propanol as porogens. The graphene-entrapped 19

monolith demonstrated better enrichment capacity compared to the parent column and 20

could be used repeatedly for at least 30 times without extraction efficiency decrease 21

[48]. A poly(ethylene glycol dimethacrylate)/graphene composite was prepared by the 22

Page 15 of 63

Accep

ted

Man

uscr

ipt

13

microwave irradiation method and used as the extraction coating of stir rod sorptive 1

extraction (SRSE). The though pore size of graphene-polymer composite was found 2

to be around 1.4 mm and the pore size distribution was narrow, which was favorable 3

for mass transfer during extraction applications. The extracted PAHs with 4

graphenepolymer composite coating compared to those with neat polymer coating 5

were in the range from 0.91 to 1.47 for 16 PAHs and no cracking of the 6

graphene-polymer composite coating was observed during stirring [49]. Graphene has 7

also been applied in pretreating solid samples, including soil, tree bark and fish, in 8

matrix solid-phase dispersion (MSPD). Grinding the solid samples with graphene 9

powder yielded a tight contact and sufficient dispersion of the sample matrix due to 10

the large surface area and flexible nanosheet morphology of graphene. Better 11

recoveries, especially for hydroxylated PBDEs, were obtained with graphene MSPD 12

than with other sorbents (e.g., C18 silica, Florisil or carbon nanotubes) and other 13

extraction techniques (e.g., Soxhlet or accelerated solvent extraction) [50]. 14

The extraction can be carried simply by dispersing graphene or graphene oxide in 15

sample solution followed by collecting the analyte-adsorbed graphene or graphene 16

oxide by centrifugation. However, it is also difficult to completely collect the 17

miniscule graphene or graphene oxide from a well-dispersed solution even by 18

high-speed centrifugation and aggregation may occur during the isolation process. 19

The group of Dong prepared several materials to resolve these issues and possess their 20

unique property. TiO2/graphene composites were synthesized through a one-step 21

hydrothermal reaction to selectively capture phosphopeptides from peptide mixtures 22

Page 16 of 63

Accep

ted

Man

uscr

ipt

14

for MALDI-TOF MS [51]; Graphene@SiO2@poly(methyl methacrylate) was 1

prepared by coupling a sol-gel method with aqueous-phase radical polymerization to 2

enrich low-abundance peptides [52]; and C8-modified graphene@mSiO2 was 3

synthesized through by coating mesoporous silica onto graphene through a 4

surfactant-mediated co-condensation sol-gel process and utilized for size selectively 5

and specifically enriching peptides in standard peptide mixtures and endogenous 6

peptides in mouse brain tissue [53]. Liu et al. assembled graphene oxide on 7

(3-aminopropyl) triethoxysilane modified SiO2 surface with -NH2 group. At pH 7, this 8

material can be used to selective extract hemoglobin from human blood and exhibited 9

favorable biocompatibility [54]. 10

11

3. Nanodiamonds 12

Diamond is an extraordinary material because of its chemical inertness, hardness, 13

high thermal conductivity, biocompatibility and optical transparency, and the 14

synthetic diamond or nanodiamond has become relatively inexpensive. Diamond’s 15

chemical inertness and hardness make it an ideal material in a number of applications, 16

e.g., as a stationary phase/support for SPE, HPLC and capillary ultrahigh pressure 17

liquid chromatography. There are no functional groups on the surface of the common 18

synthetic nanodiamond. However, a nanodiamond can be coated with a functional 19

polymer or be functionalized with hydrogen/deuterium-terminated, halogenated, 20

aminated, hydroxylated, and carboxylated surfaces by strong reagents and under 21

severe conditions. Its surface can be further modified with diverse functional groups 22

Page 17 of 63

Accep

ted

Man

uscr

ipt

15

according to targeted applications and desired physicochemical properties [55]. 1

Researches of Chen and co-workers showed that the 100 nm diamond surface could 2

be functionalized by strong oxidative acids, which left carboxyl, carbonyl and other 3

oxidized functional groups on the diamond surface. Approximate 7% of the total 4

surface carbon atoms were oxidized to form carboxyl groups determined by 5

conductometric titration [56]. The carboxylated/oxidizated diamonds were used for 6

solid-phase extraction of proteins [57], proteomes [58] or neutral glycans [59] due to 7

the interplay of electrostatic forces, hydrogen bonding and hydrophobic interactions 8

between the adsorbate and surface. Polylysine-coated diamond nanoparticles were 9

utilized for the extraction and enrichment of cytochrome c (as shown in Fig. 3.) [60], 10

DNA oligonucleotides [61]or protein digests [62], and the polyarginine-coated 11

diamonds were used for selective SPE of multiphosphorylated peptides [56]. 12

Biomolecule analytes can be easily captured by diamonds in highly diluted or/and 13

contaminated solution, separated simply by elution and centrifugation and directly 14

analyzed by matrix-assisted laser desorption/ionization mass spectrometry, which 15

enhanced the sensitivity by up to two orders of magnitude. High-throughput analysis 16

can be achieved by filtration through paraffin-coated polyvinylidenedifluoride 17

membrane filters instead of centrifugation [62]. Functionalized diamond nanoparticles 18

were also applied by this group to selectively extract and enrich multiphosphorylated 19

peptides from nonfat milk [56], and proteome analysis of blood serum [57] and 20

human urine [58]. 21

Silica is the dominant support material employed in SPE. However, silica-based 22

Page 18 of 63

Accep

ted

Man

uscr

ipt

16

column is generally only used once and functions well only at moderate pH since 1

silicon dissolves under basic conditions and can lose functionality under acidic 2

conditions. In order to improve the stability and reusability of the SPE columns, 3

Linford’s research group synthesized two series of chemically modified diamond 4

materials for SPE: amino-modified and hydrogen/deuterium-terminated diamond. 5

These SPE materials were stable under extremely acidic and basic conditions (38 h 6

exposure to 2.5 M HCl or 2.5 M NaOH solutions) attributed to diamond’s chemical 7

inertness and the reusability of the columns was assessed with satisfied results. 8

Amine-functionalized diamond was prepared by treating clean diamonds with 9

polyallylamine (PAAm) and stabilized by thermal curing or chemical crosslinking 10

[63]. It can be further functionalized by reacting with octadecyl isocyanate, and other 11

isocyanates, which creates a urea linkage from the primary amine groups. The percent 12

recoveries of the C18 functionalized diamond column for diazinon and cyanazine were 13

97.3% and 101%, respectively [64]. Porous solid diamond SPE particles were also 14

synthesized by layer-by-layer deposition of PAAm and 10-250 nm nanodiamond on 15

core particles, 30μm diamond. The density of nanodiamond particles at the surface 16

increased with the number of PAAm nanodiamond bilayers [65]. 17

Hydrogen/deuterium-terminated diamond was reacted with di-tert-amyl peroxide 18

through ether linkages as following reactions and polymer, 19

diamond-(OC(CH2)2CH(CH3))n-H, could be formed by repeated exposure of the 20

substrate to this reagent. This material was packed in a column for solid phase 21

extraction for cyanazine [66]. 22

Page 19 of 63

Accep

ted

Man

uscr

ipt

17

(CH3CH2(CH3)2CO)2 ·OC (CH3)2 CH2 CH3 1

Diamond-(H or D) + ·OC (CH3)2 CH2 CH3 2

Diamond-· + (H or D)OC (CH3)2 CH2 CH3 3

Diamond-· + ·OC (CH3)2 CH2 CH3 Diamond-OC (CH3)2 CH2 CH3 4

Diamond-OC (CH3)2 CH2 CH3+ ·OC (CH3)2 CH2 CH3 5

Diamond-(OC(CH2)2CH(CH3))n-H 6

Polystyrene encapsulated diamond was prepared by direct polymer attachment to 7

hydrogen and deuterium-terminated diamond surfaces using a radical initiator 8

(di-tert-amyl peroxide), a reactive monomer (styrene) and a crosslinking agent 9

(divinylbenzene). After surface derivatization, polystyrene-functionalized diamond 10

was sulfonated by immersion in acetic acid and concentrated sulfuric acid at 90 ◦C for 11

5 h to synthesize cation exchange SPE material. The coverage of 101% was obtained 12

for 1-naphthylamine with the sulfonated SPE columns. The columns could be used 13

multiple times without any sign of degradation [67]. 14

Hydrogen-terminated diamond surfaces were also linked with glycidyl 15

methacrylate through ultraviolet light, derivatized with iminodiacetic acid and loaded 16

with copper ions as described by Najam-ul-Haq. The capability, capacity, efficiency 17

and reproducibility of this nano-structured diamond were validated by human serum 18

sample analysis through MALDI-TOF MS for protein profiling [68, 69]. Adsorption 19

characteristics of a nanodiamond, with a mean particle size of 4 nm and prepared by 20

the detonation, for oxoacid anions was studied and it was applied to a selective 21

preconcentration method for tungstate in water samples [70]. 22

(1)

(2)

(3)

(4)

Page 20 of 63

Accep

ted

Man

uscr

ipt

18

1

4. Carbon nanofibers 2

Carbon nanofibers (CNFs) are solid carbon fibers with lengths in the order of a few 3

microns and diameters below 100 nm. CNFs differ from CNTs in the absence of a 4

hollow cavity, and the diameters of CNFs are generally higher than those of the 5

corresponding CNTs. CNFs are still very attractive because they have a relatively 6

high specific surface, and uniform mesoporous magnitude and distribution. Carbon 7

nanofibers is reported up to 1877 m2 g-1 of a specific surface area, among the highest 8

ever reported for nanostructured materials [71]. It is expected that carbon nanofibers 9

would exhibit an excellent sorptive capacity and be used as the sorbent material for 10

sample pre-concentration, as listed in Table 2. In addition, CNFs could be easily 11

available on a large scale and their surface properties can be modified with chemical 12

treatments to satisfy some special needs. CNFs have attracted great attention in the 13

applications such as gas adsorbents and catalyst supports owing to their large specific 14

surface, high chemical stability and unique mechanical properties. 15

Carbon nanoparticles, such as CNTs and graphene, tend to aggregate, which 16

hampers their application in a flow-through packed-bed mode due to an undue 17

pressure drop and deteriorated retention efficiency. Because of their significantly 18

larger dimensions, carbon nanofibers can overcome this drawback without 19

functionalization, coating or decoration. Boonjob successfully used CNFs (diameter: 20

70-150 nm, length: >20 μm) in a dedicated stirred-flow sorptive microchamber 21

integrated in a fully automated sequential injection (SI) assembly in microsolid-phase 22

Page 21 of 63

Accep

ted

Man

uscr

ipt

19

extraction (μSPE, as shown in Fig. 4.) for triazine herbicides [72]. Increasing the mass 1

of CNFs up to 80 mg was proven not to cause an increase of pressure drop in the 2

devised flow-through configuration and leaking and accumulation of CNFs onto the 3

LC precolumn was not detected at any instance in contrast to CNT-based extraction. 4

A major asset of the proposed assembly was the potential reuse of the dispersed CNFs 5

without a loss of retention efficiency for a given number of assays, while packed 6

MWCNTs SPE cartridges were recommended for single use because of their strong 7

sorption properties toward concomitant soil components. 8

Polar groups, such as carboxyl, hydroxyl and carbonyl, can be introduced on the 9

surface of carbon nanofibers by treatment with the concentrated nitric acid. The 10

treated CNFs as a solid phase extraction sorbent in microcolumn were developed for 11

preconcentration and separation of inorganic ion species, such as trace elements 12

(As(III), Cr(III), Mn(II), Mn(VII), Co(II) and Ni(II)), trivalent precious metals (Au 13

and Pd) and trace rare earth elements (La, Ce, Sm, Eu, Dy, Y, Dd and Yb), prior to 14

determination by inductively coupled plasma mass spectrometry. The adsorption 15

capacities of the treated materials that were calculated from the breakthrough curve 16

were 0.3-2.0 mg g-1 for trace elements and 11.1-23.6 mg g-1 for trivalent precious 17

metals or trace rare earth elements. The column can be reused after regeneration and 18

stable up to more than 30 adsorption-elution cycles without an obvious decrease in the 19

adsorption capacities and the recoveries for the analytes [73-79]. The adsorption of 20

metal ions strongly depended on the pH of the solution, which affected the surface 21

charge of the CNFs and the degree of ionization and speciation of the adsorbants. At 22

Page 22 of 63

Accep

ted

Man

uscr

ipt

20

the select pH value, As(III) or Cr(III) was retained on the CNFs with an adsorption 1

percentage above 90%, while As(V) or Cr(VI) passed directly through the column 2

without retention under same condition. Therefore, As(III) or Cr(III) could be 3

effectively separated from As(V) or Cr(VI) on CNFs by selection of a proper pH [78, 4

79]. 5

Electrospinning relies on repulsive electrostatic forces to draw a viscoelastic 6

solution into nanofibers, which has emerged as the most versatile technique for 7

nanofiber fabrication [80]. A polymeric negative photoresist, SU-8 2100, was used for 8

the polymer solution used to electrospin fibers and stainless steel wires were used as 9

the collector for the electrospun nanofibers. Fibers were then exposed to UV radiation 10

to crosslink onto the stainless steel, so attachment was without the use of a binder. 11

The temperatures of 400, 600, and 800 ◦C were chosen as pyrolysis temperatures for 12

the carbonization process [81, 82]. The fiber coating mass increased with the 13

electrospinning time and decreased linearly with increasing carbonization temperature. 14

The extraction characteristics of electrospun nanofibers were investigated for 15

nonpolar, polar and nonvolatile analytes. The electrospun nanofiber-coated SPME 16

fibers demonstrated superior extraction efficiencies, especially for the 600, and 800 ◦C 17

carbonization fibers, which were 1-32 times higher than a commercially available 18

SPME fiber. These SPME fibers showed the improved thermal and chemical stability, 19

and these coatings exhibited prolonged fiber lifetimes and withstood up to 100 direct 20

extractions without significant damage or change in nanofiber morphology. 21

Carbon nanofibers can also be obtained from soot by burning natural oil and 22

Page 23 of 63

Accep

ted

Man

uscr

ipt

21

extracted by tetrahydrofuran. The isolated CNFs were of 20-50 nm in diameter and 1

several micrometers in length. This carbon nanofibers were mixed with poly(vinyl 2

alcohol), PVA, and electrospun to get the 5% CNFs/PVA mat. The electrospun 3

CNF/PVA composite membrane has been developed as a sorbent material for 4

micro-extraction of aniline compounds in wastewater effluent samples [83]. 5

6

5. Carbon nanocones/disks and nanohorns 7

Carbon nanocones were first synthesized by vapor condensation of carbon atoms on 8

a graphite substrate in 1994 [84] and the fifth allotropic forms were identified in 1997 9

[85]. The disclination of each structure corresponds to the presence of a given number 10

of pentagons in the seed from which it grew: disks (no pentagons), five types of cones 11

(one to five pentagons, as shown in Fig. 5) and open tubes (six pentagons). The 12

unique electronic distribution, which is provided by these pentagonal rings to the 13

carbon nanocones, results in an enhanced local density at the cone apex. 14

Jiménez-Soto et al. [86] used purified commercial carbon nanocones/disks in SPE 15

cartridges to determinate chlorophenols in water samples. The commercial materials 16

consist of 20 wt% carbon nanocones, 70 wt% carbon disks and 10 wt% carbon black. 17

The reversibility of the analyte-sorbent interaction can be increased by thermal 18

treatment at 450 ◦C for 20 min to reduce amorphous carbon content which gave rise to 19

irreversible interactions and lower recovery values. The conical nanomaterials proved 20

to be more efficient in the preconcentration process with lower sorbent amounts for its 21

lower aggregation tendency than the carbon nanotubes [87]. The thermal treated 22

Page 24 of 63

Accep

ted

Man

uscr

ipt

22

nanocones/disks materials were also immobilized on a stainless steel needle by means 1

of an organic binder to evaluate headspace solid-phase microextraction for several 2

volatile organic compounds. The use of two layers of the carbon nanocones/disks 3

paste was sufficient to obtain a homogeneous sorbent surface and the obtained fiber 4

coating was approximate 50μm of thickness and 35mm in length. The proposed 5

method was adequate to achieve its aim with an average recovery of about 92% and 6

the LOD at nanogram per milliliter level [88]. 7

One major class of cone structures, single-walled carbon nanohorns (SWNHs), 8

narrowest opening angle with five pentagonal rings in its apex, easily form stable 9

aggregates by van der Waals forces. In 1999, it was found that about 2000 single wall 10

carbon nanohorns assembled to form roughly spherical aggregates of three types: 11

dahlias, buds and seeds [89, 90]. The dahlia-type aggregates have spherical forms 12

with diameters of about 80-100 nm, which can be produced in large quantities with 13

high purity and this structure provides high porosity and large surface area [91]. 14

SWNHs present high affinity for organic compounds with a large adsorbing capacity 15

and have been described as sorbents for ethanol, oxygen, nitrogen and water vapor. 16

SWNHs in a conventional SPE cartridge were attempted to enrich PAHs in water 17

samples. However, the extraction efficiency was very low because it was difficult to 18

maintain the nanoparticles in the low part of the cartridge and they tended to be 19

deposited on the walls [92, 93]. Oxidized single-walled carbon nanohorns were 20

proposed as the sorbent in dispersive micro solid-phase extraction for polycyclic 21

aromatic hydrocarbons and less aromatic compound, triazines, in water samples. 22

Page 25 of 63

Accep

ted

Man

uscr

ipt

23

SWNHs were functionalized by microwave energy (800 W, 10 min) to generate 1

oxygenated functional groups on the nanoparticle surface, which could facilitate their 2

dispersion in polar media. The dispersed nanoparticles were stable for more than 24 h. 3

It was better than the use of a surfactant for dispersion strategy since the core of the 4

micelles can reduce dimensions of the SWNHs and reduce enrichment efficiency. The 5

vortex was the better method than magnetic stirring and ultrasound to facilitate the 6

homogeneous interactions of the nanoparticles and analytes. Oxidized SWNHs were 7

the best sorbent in dispersive μ-SPE for all the PAHs comparing to thermally treated 8

carbon nanocones and carboxylated single-walled carbon nanotubes under the 9

optimized conditions of the method. 10

Single-walled carbon nanohorns can be used to modify glassy carbon electrode 11

(GCE) as solid-phase extraction sorbent for 4-nitrophenol. Compared with bare 12

GCE and MWCNT-modified GCE, the SWCNH-modified GCE increased the 13

sensitivity by 51.6 times and 5.55 times, respectively. The SWCNH-modified GCE 14

has excellent stability after 200 times’ measurement [94, 95]. 15

16

6. Fullerenes 17

Fullerenes, discovered in 1985 through spectrometric measurements on the 18

interstellar dust [96], are closed-cage carbon molecules containing pentagonal and 19

hexagonal rings. They have the formula C20+m, with m being an integer number, and 20

comprise a wide range of isomers and homologous series, from the most studied C60 21

and C70 to the so-called higher fullerenes like C240, C540 and C720. The relatively high 22

Page 26 of 63

Accep

ted

Man

uscr

ipt

24

electron affinity, hydrophobic surface and high surface/volume ratio of fullerenes 1

bestow their adsorption capacity towards organic molecules, which makes them ideal 2

for extraction procedures as listed in Table 3. Modified fullerenes increase the 3

selectivity associated with impregnated chemical groups. 4

The group of Gallego used fullerenes, C60 or C70, as sorbent material in an on-line 5

SPE extraction system for preconcentration of trace metal species, such as Pb[97, 98], 6

Cu [99], Cd [100], Ni [101], Co [102], and Hg [103] by forming neutral chelates. 7

Firstly, metallic species were converted to neutral chelates for quantitative retention 8

on a fullerene minicolumn by different ligands (ammonium 9

pyrrolidinedithiocarbamate or sodium diethylcarbamate). After retained, the final 10

species were eluted with the appropriate solvent and analyzed by atomic absorption 11

spectrometry. Fullerenes were more effective in pre-concentrating trace metal species 12

than C18 bonded silica, activated carbon or ion-exchange resins as sorbents in this 13

system. The continuous flow extraction systems were modified by this research group 14

to apply in the speciation of different organometallic compounds, such as metalocenes 15

[104], metallothioneins [105], metal dithiocarbamates [106] and metal alkyl species 16

[103, 107-110]. Additionally, they were also used in pre-concentration of organic 17

species, such as BTEX compounds (benzene, toluene, ethylbenzene, and xylene 18

isomers) [111], aromatic and non-aromatic N-nitrosamines [112]. The group of 19

Gallego also prepared two fullerene derivatives, C60-sodium diethyldithiocarbamate 20

and C60-rubeanic acid, for the speciation of lead or copper. The derivatives were 21

synthesized by photochemical reaction of C60 and sodium diethyldithiocarbamate or 22

Page 27 of 63

Accep

ted

Man

uscr

ipt

25

rubeanic acid in a toluene-ethanol medium. C60 was covalently bonded to classical 1

chelating reagents, and these derivatives exhibited high stability from pH 1 to 11 and 2

can be reused for at least 6 months [98, 113]. 3

Agrawal synthesized N-phenyl-(1,2-methanofullerene C60)61-formohydroxamic 4

acid, and applied it in liquid-liquid extraction (LLE) of vanadium [114], lanthanum or 5

cerium [115] and supercritical fluid extraction (SFE) of uranium [116] from different 6

substrates with satisfied results. Furthermore, Agrawal [117] also coupled it with 7

poly(styryl-β-hydroxylamine) to get poly(β-styryl)-(1,2-methanofullerene-C60)-61- 8

formohydroxamic acid and used it as solid-phase extraction of lanthanides. These rare 9

earth elements can be separated one by one from their mixtures by proper adjustment 10

of pH and judicious choice of the eluents. 11

The group of Wu immobilized polymeric fullerene [118, 119] or hydroxyfullerene 12

(fullerol) [120] on treated fused-silica fiber with a polysiloxane as backbone. The 13

synthesized fibers were used as headspace solid-phase microextraction for BTEX, 14

PCBs or PAHs and gave results that were superior to those from commercial PDMS 15

fiber. These fibers demonstrated high thermal stability and can be reused for more 16

than 150 times. 17

Different fullerene derivatives were synthesized to enrich biomolecules for mass 18

spectrometry analysis. Vallant et al. prepared C60-fullerene bound silica (C60-silica) by 19

C60-fullerenoacetic acid or C60-epoxyfullerenes covalently bounding to aminopropyl 20

linker modified silica particles as shown in Fig. 6. C60-epoxyfullerenes were chosen as 21

the final materials due to their easy handling, less time-consuming, and cost efficiency 22

Page 28 of 63

Accep

ted

Man

uscr

ipt

26

[121]. C60-silica was applied in desalting and preconcentration of proteins and 1

peptides and comparable with commercial products, such as Oasis HLB or Sep-Pak, 2

C60-silica was better than C18- or C30-silica with regards to recoveries at low peptide 3

concentrations [122]. C60-silica was also packed in SPE cartridges to enrich Amadori 4

peptides and its efficacy was competitive with commercial ZipTip, which was better 5

than C18-silica [123]. Vallant et al. [124] also synthesized dioctadecyl 6

methano(60)fullerene, (60)fullerenoacetic acid and iminodiacetic acid(60)fullerene. 7

(60)fullerenoacetic acid was the most effective carrier material for selective 8

enrichment of low-mass serum constituents. 9

C60-functionalized magnetic silica microspheres were prepared by radical 10

polymerization of C60 molecules on 3-(trimethoxysilyl)propyl methacrylate modified 11

magnetic silica microspheres. Due to magnetic properties and admirable adsorption, 12

this magnetic material can make enrichment and desalting of low-concentration 13

peptides or proteins from complex biological samples fast, convenient and efficient 14

[125]. 15

Fullerene derivatives were also used as ion-pair reagents for selective precipitation 16

of biomolecules for mass spectrometry analysis. A starlike water-soluble 17

hexa(sulfonbutyl) fullerene was synthesized to selectively precipitate positively 18

charged surfactants or biomolecules and used as the MALDI matrix to directly 19

characterize the analytes precipitated by the ionic sulfonate arms. The affinity of the 20

material to the analytes depends on charge, structure, and hydrophobicity of the 21

analytes [126]. Lee et al. [127] prepared water-soluble 22

Page 29 of 63

Accep

ted

Man

uscr

ipt

27

C60-N,N-dimethylpyrrolidinium iodide for selectively precipitating the 4-sulfophenyl 1

isothiocyanate-modified peptides by forming a noncovalent ion pair. The ion-pair 2

precipitate can be removed from the sample solution by centrifugation and easily 3

resuspended using an acid solution. 4

5

7. Carbon nanotubes 6

Carbon nanotubes (CNTs), discovered in 1991 by Iijima [128], have diameters 7

from fractions to tens of nanometers and lengths up to several micrometers. CNTs can 8

be considered as a graphene sheet in the shape of a cylinder capped by fullerene-like 9

structures. Single-walled (SWCNTs) and multi-walled (MWCNTs) nanotubes are 10

formed by seamless roll up of single and multi layers of graphene lamella respectively. 11

Their reported surface areas range from 150 to 1500 m2 g-1, which is a basis for 12

serving as good sorbents [129]. Furthermore, CNTs can be easily covalently or 13

non-covalently functionalized with different organic molecules to provide a more 14

selective interaction with analytes. Until now, CNTs have been the most used 15

carbon-based nanomaterials in sample preparation, and hundreds of research articles 16

and tens of critical review papers are available in this field[2, 130, 131]. Only the 17

most influential of them are described here because of length limit of this review. 18

The research group of Jiang first packed multiwalled carbon nanotubes into 19

commercial SPE cartridge or disk for solid-phase extraction of organic pollutants 20

from aqueous samples [132, 133]. Since then, different types of CNTs, including 21

non-functionalized or modified MWCNTs, and SWCNTs, were used as packing 22

Page 30 of 63

Accep

ted

Man

uscr

ipt

28

materials for preconcentration of phenolic compounds, pesticides, pharmaceuticals, 1

inorganic ions and organometallic compounds in food, in environmental samples, or 2

in biofluids, which were summarized in the review papers [134-136]. The excellent 3

features of CNTs make them ideal sorbents in different micro-concentrators or 4

micro-sorbent traps, which were reviewed by Hussain and Mitra [129]. 5

The CNTs-SPME fibers were prepared through several procedures including sol-gel 6

technology (the most widely used one), chemical bonding, electrochemical 7

polymerization, electrophoretic deposition, physical agglutination by an organic 8

binder, atom transfer radical polymerization and magnetron sputtering. The fiber 9

materials used in CNTs-SPME can be fused silica, hollow fiber, stainless steel, gold or 10

platinum wire to acquire special properties [129, 134, 135]. 11

After oxidation under extreme conditions, CNTs possess hydroxyl, carboxyl and 12

carbonyl groups on their surface and show exceptional adsorption efficiency for metal 13

removal when the solution pH is higher than the isoelectric point of the oxidized 14

CNTs. Oxidized CNTs can be used as extraction materials for metallic compounds 15

previous to their analytical determination [131, 134]. Oxidized CNTs can be grafted 16

with function groups (e.g., amines, esters, alkyl chains and polymers) via creation of 17

amide bonds, N2-plasma technique and radical addition with aryl-diazonium salts to 18

efficiently or/and selectively pre-concentrate trace metal ions as described in the 19

review paper of Sitko et al. [137]. 20

Molecularly imprinted polymer (MIPs) can be introduced on the surface of CNTs 21

to selectively extract organic analytes. CNTs, which were used as MIPs supporting 22

Page 31 of 63

Accep

ted

Man

uscr

ipt

29

materials, can greatly improve accessibility of the template molecule, reduce the 1

binding time and enhance the extraction efficiency [135]. 2

Carbon nanotubes can also be readily immobilized into the pore structure of a 3

polymeric membrane, which can dramatically improve its performance in membrane 4

extraction. Here the CNTs serve as a sorbent and provide an additional pathway for 5

solute transport. The presence of CNTs increased the effective surface area and the 6

overall partition coefficient on the membrane and lead to an enhancement in the 7

analyte transport [138-140]. 8

Similar to other carbon-based materials, carbon nanotubes can be modified with 9

magnetic particles as MSPE material for enrichment of organic or trace metal analyte 10

[135, 137]. CNTs were also used to trap analyte molecules by sorption and act as an 11

energy receptacle for laser desorption/ionization in matrix-assisted LDI (MALDI) and 12

surface-assisted LDI (SALDI) MS on several occasions [135, 141, 142]. 13

14

8. Discussion 15

In order to summarize and compare above six carbon-based nanomaterials in 16

different sample preparation techniques, the distinctive characteristics, derivatization 17

methods and application techniques of these materials are listed in Table 4. The 18

research status and perspective of them also proposed according to properties of 19

materials, the number of published articles and publication year, and they are visually 20

illustrated by the star number. Four groups were classified based on the description of 21

Table 4. 22

Page 32 of 63

Accep

ted

Man

uscr

ipt

30

The first group will be graphene and carbon nanotubes. They can be easily 1

synthesized or available and they could covalently or non-covalently functionalized 2

via graphene oxide or oxidized CNTs to satisfy some special needs. They have been 3

applied to most of sample preparation techniques based on solid adsorbents. The 4

researches on them will still be the hot spot in this field. The future trends of them 5

might be improving their use in routine application and in complex matrix samples. 6

The economic and reliable commercial products are anticipated. 7

Although there are not so many papers about carbon nanofibers in sample 8

preparation as graphene and CNTs, the articles about CNFs come up recently and 9

there are more publications about nanofibers (without carbonization process) in this 10

field. The phenomena are attributed to their larger dimensions which can avoid 11

aggregating during on-line processes without coating or functionalization. 12

Furthermore, CNFs can be available on a large scale, especially via electrospinning 13

technologies. More researches would be contributed to CNFs in different sample 14

preparation techniques. 15

The third group is fullerenes. Fullerenes were firstly applied in sample preparation 16

of these nanomaterials and more than thirty papers were published. However, almost 17

no articles were found after 2009. The phenomena might be owing to the reason that 18

the properties of fullerenes can not be comparable to other materials. 19

The last group will be nanodiamonds, carbon nanocones/disks and nanohorns. 20

Since these nanomaterials can not be easily available as other materials, there are 21

limited groups which focus on these researches. Almost all papers about carbon 22

Page 33 of 63

Accep

ted

Man

uscr

ipt

31

nanocones/disks and nanohorns were from the research group of Valcárcel and the 1

publicaions about nanodiamonds were dominant by the goups of Chang and Linford. 2

3

9. Conclusions 4

Owing to their special properties, carbon-based nanomaterials have found a wide 5

range of applications in different sample preparation technologies: they can be used as 6

sorbent agents, such as SPE or on-line SPE, by direct interaction between the analyte 7

and the nanoparticles; they can be immobilized on fibers as SPME; they can have 8

special magnetic properties, so the use of a magnetic field can help simplify the 9

analytical procedure; they can act as an inert support, such as for molecularly 10

imprinted polymer; and they can also act as ionization agents for the enrichment and 11

direct analysis of samples by LDI mass spectrometry. 12

Furthermore, sample preparation technologies based on these carbon nanomaterials 13

have more advantages than conventional materials. For example, the SPME fibers, 14

coating with graphene, CNTs or CNFs demonstrated superior extraction efficiencies, 15

which were several times higher than a commercially available SPME fiber. These 16

SPME fibers showed the improved thermal and chemical stability, and the coatings 17

exhibited prolonged fiber lifetimes. The SPE materials based on nanodiamonds were 18

stable under extremely acidic and basic conditions and the reusability of the columns 19

was assessed with satisfied results. More challenging and interesting publications 20

about carbon nanomaterials will surely appear in this attractive analytical field in the 21

forthcoming years, especially for graphene, CNTs and CNFs. 22

Page 34 of 63

Accep

ted

Man

uscr

ipt

32

The economical viability of carbon nanomaterials will be a key aspect for 1

broadening their use. Although carbon nanomaterials are economically attainable for 2

research purposes, their use in routine laboratories is still limited. Furthermore, 3

modifications make the product more expensive. Therefore, limited reliable 4

commercial sources of carbon nanomaterials are available for sample preparation. 5

6

Acknowledgements 7

The authors acknowledge financial supports from the Specific Research on Public 8

Service of Environmental Protection in China (No. 201009009), National Natural 9

Science Foundation of China (No. 21275088) and New Century Excellent Tales in 10

University (NCET-09-0230). 11

12

13

Page 35 of 63

Accep

ted

Man

uscr

ipt

33

References 1

[1] G. Lasarte-Aragonés, R. Lucena, S. Cárdenas, M. Valcárcel, Bioanalysis 3 (2011) 2

2533-2548. 3

[2] K. Scida, P.W. Stege, G. Haby, G.A. Messina, C.D. García, Anal. Chim. Acta 691 4

(2011) 6-17. 5

[3] K.S. Novoselov, A.K. Geim, S.V. Morozov, D. Jiang, Y. Zhang, S.V. Dubonos, I.V. 6

Grigorieva, A.A. Firsov, Science 306 (2004) 666-669. 7

[4] K.S. Novoselov, V.I. Fal'ko, L. Colombo, P.R. Gellert, M.G. Schwab, K. Kim, 8

Nature 490 (2012) 192-200. 9

[5] Q. Liu, J. Shi, L. Zeng, T. Wang, Y. Cai, G. Jiang, J. Chromatogr. A 1218 (2011) 10

197-204. 11

[6] J. Qu, H. Chen, C. Lu, Z. Wang, J.-M. Lin, Analyst, 137 (2012) 1824-1830. 12

[7] X. Lin, H.-F. Li, X. He, Y. Hashi, J.-M. Lin, Z. Wang, J. Sep. Sci., 35 (2012) 13

2553-2558. 14

[8] Q. Chang, S. Song, Y. Wang, J. Li, J. Ma, Anal. Methods 4 (2012) 1110-1116. 15

[9] Y. Wang, S. Gao, X. Zang, J. Li, J. Ma, Anal. Chim. Acta 716 (2012) 112-118. 16

[10] K.-J. Huang, Q.-S. Jing, C.-Y. Wei, Y.-Y. Wu, Spectrochim. Acta A 79 (2011) 17

1860-1865. 18

[11] K.-J. Huang, S. Yu, J. Li, Z.-W. Wu, C.-Y. Wei, Microchim. Acta 176 (2012) 19

327-335. 20

[12] Q. Liu, J. Shi, G. Jiang, Trac-Trend Anal. Chem. 37 (2012) 1-11. 21

[13] Q. Liu, J. Shi, J. Sun, T. Wang, L. Zeng, G. Jiang, Angew. Chem. -Int. Edit. 50 22

(2011) 5913-5917. 23

[14] L.-L. Wang, S. Yu, M. Yu, Spectrochim. Acta A 98 (2012) 337-342. 24

[15] L. Chen, T. Wang, J. Tong, Trac-Trends Anal. Chem. 30 (2011) 1095-1108. 25

[16] Y. Geng, M. Ding, H. Chen, H.-F. Li, J.-M. Lin, Talanta, 89 (2012) 189-194. 26

[17] Q. Wu, M. Liu, X. Ma, W. Wang, C. Wang, X. Zang, Z. Wang, Microchim. Acta, 27

177 (2012) 23-30. 28

[18] G. Zhao, S. Song, C. Wang, Q. Wu, Z. Wang, Anal. Chim. Acta 708 (2011) 29

Page 36 of 63

Accep

ted

Man

uscr

ipt

34

155-159. 1

[19] Q. Wu, G. Zhao, C. Feng, C. Wang, Z. Wang, J. Chromatogr. A 1218 (2011) 2

7936-7942. 3

[20] W. Wang, X. Ma, Q. Wu, C. Wang, X. Zang, Z. Wang, J. Sep. Sci. 35 (2012) 4

2266-2272. 5

[21] W. Wang, Y. Li, Q. Wu, C. Wang, X. Zang, Z. Wang, Anal. Methods 4 (2012) 6

766-772. 7

[22] C. Shi, J. Meng, C. Deng, Chem. Commun. 48 (2012) 2418-2420. 8

[23] Y.-B. Luo, Z.-G. Shi, Q. Gao, Y.-Q. Feng, J. Chromatogr. A 1218 (2011) 9

1353-1358. 10

[24] Q. Liu, J. Shi, M. Cheng, G. Li, D. Cao, G. Jiang, Chem. Commun. 48 (2012) 11

1874-1876. 12

[25] Q. Liu, J. Shi, T. Wang, F. Guo, L. Liu, G. Jiang, J. Chromatogr. A 1257 (2012) 13

1-8. 14

[26] C. Shi, J. Meng, C. Deng, J. Mater. Chem. 22 (2012) 20778-20785. 15

[27] C.L. Arthur, J. Pawliszyn, Anal. Chem. 62 (1990) 2145-2148. 16

[28] G. Huang, H.-F. Li, B.-T. Zhang, Y. Ma, J.-M. Lin, Talanta, 100 (2012) 64-70. 17

[29] J. Chen, J. Zou, J. Zeng, X. Song, J. Ji, Y. Wang, J. Ha, X. Chen, Anal. Chim. 18

Acta 678 (2010) 44-49. 19

[30] G. Zhao, S. Song, C. Wang, Q. Wu, Z. Wang, Anal. Methods 3 (2011) 2929-2935. 20

[31] Q. Wu, C. Feng, G. Zhao, C. Wang, Z. Wang, J. Sep. Sci. 35 (2012) 193-199. 21

[32] V.K. Ponnusamy, J.-F. Jen, J. Chromatogr. A 1218 (2011) 6861-6868. 22

[33] J. Zou, X. Song, J. Ji, W. Xu, J. Chen, Y. Jiang, Y. Wang, X. Chen, J. Sep. Sci. 34 23

(2011) 2765-2772. 24

[34] H. Zhang, H.K. Lee, Anal. Chim. Acta 742 (2012) 67-73. 25

[35] H. Zhang, H.K. Lee, J. Chromatogr. A 1218 (2011) 4509-4516. 26

[36] S. Zhang, Z. Du, G. Li, J. Chromatogr. A 1260 (2012) 1-8. 27

[37] L. Xu, J. Feng, J. Li, X. Liu, S. Jiang, J. Sep. Sci. 35 (2012) 93-100. 28

[38] S. Zhang, Z. Du, G. Li, Anal. Chem. 83 (2011) 7531-7541. 29

[39] X. Dong, J. Cheng, J. Li, Y. Wang, Anal. Chem. 82 (2010) 6208-6214. 30

Page 37 of 63

Accep

ted

Man

uscr

ipt

35

[40] J. Zhang, X. Dong, J. Cheng, J. Li, Y. Wang, J. Am. Soc. Mass Spectrom. 22 1

(2011) 1294-1298. 2

[41] Y. Liu, J. Liu, P. Yin, M. Gao, C. Deng, X. Zhang, J. Mass Spectrom. 46 (2011) 3

804-815. 4

[42] Y. Liu, J. Liu, C. Deng, X. Zhang, Rapid Commun. Mass Spectrom. 25 (2011) 5

3223-3234. 6

[43] J. Liu, Y. Liu, M. Gao, X. Zhang, J. Am. Soc. Mass Spectrom. 23 (2012) 7

1424-1427. 8

[44] L.A.L. Tang, J. Wang, K.P. Loh, J. Am. Chem. Soc. 132 (2010) 10976-10977. 9

[45] L.A.L. Tang, J. Wang, T.K. Lim, X. Bi, W.C. Lee, Q. Lin, Y.-T. Chang, C.T. Lim, 10

K.P. Loh, Anal. Chem. 84 (2012) 6693-6700. 11

[46] B. Gulbakan, E. Yasun, M.I. Shukoor, Z. Zhu, M. You, X. Tan, H. Sanchez, D.H. 12

Powell, H. Dai, W. Tan, J. Am. Chem. Soc. 132 (2010) 17408-17410. 13

[47] H. Zhang, W.P. Low, H.K. Lee, J. Chromatogr. A 1233 (2012) 16-21. 14

[48] S. Tong, Q. Liu, Y. Li, W. Zhou, Q. Jia, T. Duan, J. Chromatogr. A 1253 (2012) 15

22-31. 16

[49] Y.-B. Luo, J.-S. Cheng, Q. Ma, Y.-Q. Feng, J.-H. Li, Anal. Methods 3 (2011) 17

92-98. 18

[50] Q. Liu, J. Shi, J. Sun, T. Wang, L. Zeng, N. Zhu, G. Jiang, Anal. Chim. Acta 708 19

(2011) 61-68. 20

[51] J. Lu, M. Wang, Y. Li, C. Deng, Nanoscale 4 (2012) 1577-1580. 21

[52] P. Yin, M. Zhao, C. Deng, Nanoscale 4 (2012) 6948-6950. 22

[53] P. Yin, Y. Wang, Y. Li, C. Deng, X. Zhang, P. Yang, Proteomics 12 (2012) 23

2784-2791. 24

[54] J.-W. Liu, Q. Zhang, X.-W. Chen, J.-H. Wang, Chem.-Eur. J. 17 (2011) 25

4864-4870. 26

[55] P.N. Nesterenko, P.R. Haddad, Anal. Bioanal. Chem. 396 (2010) 205-211. 27

[56] C.-K. Chang, C.-C. Wu, Y.-S. Wang, H.-C. Chang, Anal. Chem. 80 (2008) 28

3791-3797. 29

[57] X.L. Kong, L.C.L. Huang, C.-M. Hsu, W.-H. Chen, C.-C. Han, H.-C. Chang, 30

Page 38 of 63

Accep

ted

Man

uscr

ipt

36

Anal. Chem. 77 (2005) 259-265. 1

[58] W.-H. Chen, S.-C. Lee, S. Sabu, H.-C. Fang, S.-C. Chung, C.-C. Han, H.-C. 2

Chang, Anal. Chem. 78 (2006) 4228-4234. 3

[59] Y.-K. Tzeng, C.-C. Chang, C.-N. Huang, C.-C. Wu, C.-C. Han, H.-C. Chang, 4

Anal. Chem. 80 (2008) 6809-6814. 5

[60] L.C.L. Huang, H.C. Chang, Langmuir 20 (2004) 5879-5884. 6

[61] X. Kong, L.C.L. Huang, S.-C.V. Liau, C.-C. Han, H.-C. Chang, Anal. Chem. 77 7

(2005) 4273-4277. 8

[62] X. Kong, S. Sahadevan, Anal. Chim. Acta 659 (2010) 201-207. 9

[63] G. Saini, L. Yang, M.L. Lee, A. Dadson, M.A. Vail, M.R. Linford, Anal. Chem. 10

80 (2008) 6253-6259. 11

[64] G. Saini, L.A. Wiest, D. Herbert, K.N. Biggs, A. Dadson, M.A. Vail, M.R. 12

Linford, J. Chromatogr. A 1216 (2009) 3587-3593. 13

[65] G. Saini, D.S. Jensen, L.A. Wiest, M.A. Vail, A. Dadson, M.L. Lee, V. 14

Shutthanandan, M.R. Linford, Anal. Chem. 82 (2010) 4448-4456. 15

[66] L. Yang, M.A. Vail, A. Dadson, M.L. Lee, M.C. Asplund, M.R. Linford, Chem. 16

Mat. 21 (2009) 4359-4365. 17

[67] L. Yang, D.S. Jensen, M.A. Vail, A. Dadson, M.R. Linford, J. Chromatogr. A 18

1217 (2010) 7621-7629. 19

[68] M. Najam-ul-Haq, M. Rainer, C.W. Huck, G. Stecher, I. Feuerstein, D. 20

Steinmuller, G.K. Bonn, Curr. Nanosci. 2 (2006) 1-7. 21

[69] M. Najam-ul-Haq, M. Rainer, C.W. Huck, M.N. Ashiq, G.K. Bonn, Amino Acids 22

43 (2012) 823-831. 23

[70] H. Sakurai, N. Ebihara, E. Osawa, M. Takahashi, M. Fujinami, K. Oguma, Anal. 24

Sci. 22 (2006) 357-362. 25

[71] N.-N. Bui, B.-H. Kim, K.S. Yang, M.E. Dela Cruz, J.P. Ferraris, Carbon 47 (2009) 26

2538-2539. 27

[72] W. Boonjob, M. Miró, M.A. Segundo, V. Cerdà, Anal. Chem. 83 (2011) 28

5237-5244. 29

[73] S. Chen, M. Mao, D. Lu, Z. Wang, Spectrochim. Acta B 62 (2007) 1216-1221. 30

Page 39 of 63

Accep

ted

Man

uscr

ipt

37

[74] S. Chen, M. Xiao, D. Lu, Z. Hu, X. Zhan, Atom. Spectrosc. 28 (2007) 90-94. 1

[75] S. Chen, M. Xiao, D. Lu, X. Zhan, Rapid Commun. Mass Spectrom. 21 (2007) 2

2524-2528. 3

[76] S. Chen, M. Xiao, D. Lu, X. Zhan, Anal. Lett. 40 (2007) 2105-2115. 4

[77] S. Chen, X. Zhan, D. Lu, M. Yang, Atom. Spectrosc. 29 (2008) 45-50. 5

[78] S. Chen, X. Zhan, D. Lu, M. Yang, C. Liu, Atom. Spectrosc. 29 (2008) 124-128. 6

[79] S. Chen, X. Zhan, D. Lu, C. Liu, L. Zhu, Anal. Chim. Acta 634 (2009) 192-196. 7

[80] S. Chigome, G. Darko, N. Torto, Analyst 136 (2011) 2879-2889. 8

[81] J.W. Zewe, J.K. Steach, S.V. Olesik, Anal. Chem. 82 (2010) 5341-5348. 9

[82] T.E. Newsome, J.W. Zewe, S.V. Olesik, J. Chromatogr. A 1262 (2012) 1-7. 10

[83] S. Vadukumpully, C. Basheer, C.S. Jeng, S. Valiyaveettil, J. Chromatogr. A 1218 11

(2011) 3581-3587. 12

[84] M.H. Ge, K. Sattler, Chem. Phys. Lett. 220 (1994) 192-196. 13

[85] A. Krishnan, E. Dujardin, M.M.J. Treacy, J. Hugdahl, S. Lynum, T.W. Ebbesen, 14

Nature 388 (1997) 451-454. 15

[86] J.M. Jiménez-Soto, S. Cárdenas, M. Valcárcel, J. Chromatogr. A 1216 (2009) 16

5626-5633. 17

[87] R. Lucena, B.M. Simonet, S. Cárdenas, M. Valcárcel, J. Chromatogr. A 1218 18

(2011) 620-637. 19

[88] J.M. Jiménez-Soto, S. Cárdenas, M. Valcárcel, J. Chromatogr. A 1217 (2010) 20

3341-3347. 21

[89] S. Iijima, M. Yudasaka, R. Yamada, S. Bandow, K. Suenaga, F. Kokai, K. 22

Takahashi, Chem. Phys. Lett. 309 (1999) 165-170. 23

[90] M. Yudasaka, S. Iijima, V.H. Crespi, Top. Appl. Phys. 111 (2008) 605-629. 24

[91] J.M. Jiménez-Soto, Y. Moliner-Martínez, S. Cárdenas, M. Valcárcel, 25

Electrophoresis 31 (2010) 1681-1688. 26

[92] J.M. Jiménez-Soto, S. Cárdenas, M. Valcárcel, Anal. Chim. Acta 714 (2012) 27

76-81. 28

[93] J.M. Jiménez-Soto, S. Cárdenas, M. Valcárcel, J. Chromatogr. A 1245 (2012) 29

17-23. 30

Page 40 of 63

Accep

ted

Man

uscr

ipt

38

[94] S. Zhu, W. Niu, H. Li, S. Han, G. Xu, Talanta 79 (2009) 1441-1445. 1

[95] S. Zhu, G. Xu, Nanoscale 2 (2010) 2538-2549. 2

[96] H.W. Kroto, J.R. Heath, S.C. O’brien, R.F. Curl, R.E. Smalley, Nature 318 (1985) 3

162-163. 4

[97] M. Gallego, Y.P. De Peña, M. Valcárcel, Anal. Chem. 66 (1994) 4074-4078. 5

[98] J.R. Baena, M. Gallego, M. Valcárcel, Anal. Chem. 74 (2002) 1519-1524. 6

[99] Y.P. De Peña, M. Gallego, M. Valcárcel, Anal. Chem. 67 (1995) 2524-2529. 7

[100] Y.P. De Peña, M. Gallego, M. Valcárcel, J. Anal. At. Spectrom. 12 (1997) 8

453-457. 9

[101] M.M. Silva, M.A.Z. Arruda, F.J. Krug, P.V. Oliveira, Z.F. Queiroz, M. Gallego, 10

M. Valcárcel, Anal. Chim. Acta 368 (1998) 255-263. 11

[102] M.M. González, M. Gallego, M. Valcárcel, J. Anal. At. Spectrom. 14 (1999) 12

711-716. 13

[103] J. Munoz, M. Gallego, M. Valcárcel, J. Chromatogr. A 1055 (2004) 185-190. 14

[104] E. Ballesteros, M. Gallego, M. Valcárcel, J. Chromatogr. A 869 (2000) 101-110. 15

[105] J. Muñoz, J.R. Baena, M. Gallego, M. Valcárcel, J. Anal. At. Spectrom. 17 16

(2002) 716-720. 17

[106] J.R. Baena, M. Gallego, M. Valcárcel, Analyst 125 (2000) 1495-1499. 18

[107] J.R. Baena, M. Gallego, M. Valcárcel, Spectrochim. Acta B 54 (1999) 19

1869-1879. 20

[108] J.R. Baena, S. Cárdenas, M. Gallego, M. Valcárcel, Anal. Chem. 72 (2000) 21

1510-1517. 22

[109] J. Muñoz, J. Baena, M. Gallego, M. Valcárcel, J. Chromatogr. A 1023 (2004) 23

175-181. 24

[110] J. Muñoz, M. Gallego, M. Valcárcel, Anal. Chim. Acta 548 (2005) 66-72. 25

[111] A. Serrano, M. Gallego, J. Sep. Sci. 29 (2006) 33-40. 26

[112] B. Jurado-Sánchez, E. Ballesteros, M. Gallego, J. Chromatogr. A 1216 (2009) 27

1200-1205. 28

[113] J. Muñoz, M. Gallego, M. Valcárcel, J. Anal. At. Spectrom 21 (2006) 29

1396-1402. 30

Page 41 of 63

Accep

ted

Man

uscr

ipt

39

[114] Y.K. Agrawal, Fuller. Nanotub. Carbon Nanostruct. 11 (2003) 135-154. 1

[115] Y.K. Agrawal, Fuller. Nanotub. Carbon Nanostruct. 12 (2004) 545-570. 2

[116] Y.K. Agrawal, Fuller. Nanotub. Carbon Nanostruct. 14 (2006) 621-639. 3

[117] Y.K. Agrawal, Fuller. Nanotub. Carbon Nanostruct. 15 (2007) 353-365. 4

[118] C.H. Xiao, Z.L. Liu, Z.Y. Wang, C.Y. Wu, H.M. Han, Chromatographia 52 5

(2000) 803-809. 6

[119] C. Xiao, S. Han, Z. Wang, J. Xing, C. Wu, J. Chromatogr. A 927 (2001) 7

121-130. 8

[120] J. Yu, L. Dong, C. Wu, L. Wu, J. Xing, J. Chromatogr. A 978 (2002) 37-48. 9

[121] R.M. Vallant, Z. Szabo, S. Bachmann, R. Bakry, M. Najam-ul-Haq, M. Rainer, 10

N. Heigl, C. Petter, C.W. Huck, G.K. Bonn, Anal. Chem. 79 (2007) 8144-8153. 11

[122] K. Böddi, A. Takátsy, S. Szabó, L. Markó, L. Márk, I. Wittmann, R. Ohmacht, G. 12

Montskó, R.M. Vallant, T. Ringer, R. Bakry, C.W. Huck, G.K. Bonn, Z. Szabó, J. 13

Sep. Sci. 32 (2009) 295-308. 14

[123] A. Takátsy, K. Böddi, L. Nagy, G. Nagy, S. Szabó, L. Markó, I. Wittmann, R. 15

Ohmacht, T. Ringer, G.K. Bonn, D. Gjerde, Z. Szabó, Anal. Biochem. 393 16

(2009) 8-22. 17

[124] R.M. Vallant, Z. Szabo, L. Trojer, M. Najam-ul-Haq, M. Rainer, C.W. Huck, R. 18

Bakry, G.K. Bonn, J. Proteome Res. 6 (2007) 44-53. 19

[125] H. Chen, D. Qi, C. Deng, P. Yang, X. Zhang, Proteomics 9 (2009) 380-387. 20

[126] J. Shiea, J.-P. Huang, C.-F. Teng, J. Jeng, L.Y. Wang, L.Y. Chiang, Anal. Chem. 21

75 (2003) 3587-3595. 22

[127] Y.H. Lee, J.-W. Shin, S. Ryu, S.-W. Lee, C.H. Lee, K. Lee, Anal. Chim. Acta 23

556 (2006) 140-144. 24

[128] S. Iijima, Nature 354 (1991) 56-58. 25

[129] C.M. Hussain, S. Mitra, Anal. Bioanal. Chem. 399 (2011) 75-89. 26

[130] B. Pérez-López, A. Merkoçi, Microchim. Acta, 179 (2012) 1-16. 27

[131] C. Herrero Latorre, J. Álvarez Méndez, J. Barciela García, S. García Martín, 28

R.M. Peña Crecente, Anal. Chim. Acta, 749 (2012) 16-35. 29

[132] Y. Cai, G. Jiang, J. Liu, Q. Zhou, Anal. Chem. 75 (2003) 2517-2521. 30

Page 42 of 63

Accep

ted

Man

uscr

ipt

40

[133] H.Y. Niu, Y.Q. Cai, Y.L. Shi, F.S. Wei, J.M. Liu, G. B. Jiang, Anal. Bioanal. 1

Chem. 392 (2008) 927-935. 2

[134] L.M. Ravelo-Pérez, A.V. Herrera-Herrera, J. Hernández-Borges, M.Á. 3

Rodríguez-Delgado, J. Chromatogr. A 1217 (2010) 2618-2641. 4

[135] A.V. Herrera-Herrera, M.A. González-Curbelo, J. Hernández-Borges, M.Á. 5

Rodríguez-Delgado, Anal. Chim. Acta 734 (2012) 1-30. 6

[136] K. Pyrzynska, Chemosphere 83 (2011) 1407-1413. 7

[137] R. Sitko, B. Zawisza, E. Malicka, Trac-Trends Anal. Chem. 37 (2012) 22-31. 8

[138] K. Hylton, Y. Chen, S. Mitra, J. Chromatogr. A, 1211 (2008) 43-48. 9

[139] K.S. Hasheminasab, A.R. Fakhari, Anal. Chim. Acta, 767 (2013) 75-80. 10

[140] M. Fayazi, M. Ghanei-Motlagh, M.A. Taher, Anal. Methods, 5 (2013) 11

1474-1480. 12

[141] M. Valcárcel, S. Cárdenas, B.M. Simonet, Anal. Chem. 79 (2007) 4788-4797. 13

[142] M. Najam-ul-Haq, M. Rainer, Z. Szabó, R. Vallant, C.W. Huck, G.K. Bonn, J. 14

Biochem. Biophys. Methods 70 (2007) 319-328. 15 16

17

Page 43 of 63

Accep

ted

Man

uscr

ipt

41

Figure caption 1

Fig. 1. Chemical routes to the synthesis of GO@silica and G@silica GO, graphene 2

oxide; G, graphene. [13]. 3

Fig. 2. Schematic demonstration of the fabrication processes of graphene-coated 4

SPME fiber [38]. 5

Fig. 4. Schematic illustration of the sequential injection-liquid chromatography 6

hyphenated setup for automated CNF-based microextraction and determination of 7

trace level concentrations of triazine herbicides in environmental matrixes. MPV: 8

multiposition valve; IV: injection valve; MSP: multisyringe pump; HC: holding coil; 9

CC: communication channel. The inset illustrates two designs of stirred-flow 10

chambers for μSPE [72]. 11

Fig. 5. Angles formed at the vertex of the carbon nanocones depending on the number 12

of existing pentagons [86]. 13

Fig. 6. Reaction scheme showing the synthesis of fullerene-bonded silica using (A) 14

C60-fullerenoacetic acid and (B) C60-epoxyfullerene as the starting material [121]. 15

16

Page 44 of 63

Accep

ted

Man

uscr

ipt

42

1

2

3

Fig. 1. Chemical routes to the synthesis of GO@silica and G@silica GO, graphene 4

oxide; G, graphene. [13]. 5

6

Page 45 of 63

Accep

ted

Man

uscr

ipt

43

1

2 3

Fig. 2. Schematic demonstration of the fabrication processes of graphene-coated 4

SPME fiber [38]. 5

6

Page 46 of 63

Accep

ted

Man

uscr

ipt

44

1

O

OH Poly-L-lysine

pH 8.5

O

O

N+H

H

HN

O

N+H

HH

N O

N+HH

H

O

O

N+H

H

HN

O

NH

N O

N+HH

H

O

O

N+H

H

HN

O

NH

N O

N+HH

H

N OO

DYEO

OO

DYE

N O

O

O

N

O

O

O

NaO3S

1.

2. Yeast cytochrome c (YCC)N

O

OO

YCC

2

3

Fig. 3. Reactions for surface amination, dye-labeling and protein immobilization on 4

nanodiamonds [60]. 5

6

Page 47 of 63

Accep

ted

Man

uscr

ipt

45

1

2 3

Fig. 4. Schematic illustration of the sequential injection-liquid chromatography 4

hyphenated setup for automated CNF-based microextraction and determination of 5

trace level concentrations of triazine herbicides in environmental matrixes. MPV: 6

multiposition valve; IV: injection valve; MSP: multisyringe pump; HC: holding coil; 7

CC: communication channel. The inset illustrates two designs of stirred-flow 8

chambers for μSPE [72]. 9

10

Page 48 of 63

Accep

ted

Man

uscr

ipt

46

1

2

3

Fig. 5. Angles formed at the vertex of the carbon nanocones depending on the number 4

of existing pentagons [86]. 5

6

Page 49 of 63

Accep

ted

Man

uscr

ipt

47

1

2

3

Fig. 6. Reaction scheme showing the synthesis of fullerene-bonded silica using (A) 4

C60-fullerenoacetic acid and (B) C60-epoxyfullerene as the starting material [121].5

Page 50 of 63

Accep

ted

Man

uscr

ipt

48

Table 1 Application of graphene in sample preparation Analyte Matrix Sorbent type Sample

preparation Techniques Recovery

(%) LODs Remarks References

Chlorophenols Tap and river water Graphene SPE HPLC-DAD 77.2-116.6 0.1-0.4 ng mL-1

Packing in a cartridge

[5]

Cr(III) Water (tap, sea and river)

Graphene SPE FAAS 95.7-101.2 0.5 μg L-1 Packing in a column [8]

Pb Water (tap, sea and river) and vegetable

Graphene SPE FAAS 95.3-100.4 0.61 μg L-1 Packing in a column [9]

Glutathione Human plasma Graphene SPE FL 92-108 0.01 nM Packing in a column [10] Neurotransmitters Rat brain Graphene SPE HPLC-FL 94.2-112.1 23.4-67.5 ng

g-1 Packing in a column; EF, 118-152

[11]

Chlorophenols, hydroxylated or polybrominated diphenyl ethers

Aqueous or hexane solutions, protein mixture

Graphene @Silica

SPE HPLC-UV, HPLC-MS/MS, MALDI-TOF MS

82.4-105.1 —

Packing in a cartridge

[13]

S-nitrosothiols

Blood samples

TiO2- graphene

SPE FL

92.0-104.0 0.08 nM

Packing in a cartridge

[14]

Phthalate esters Water (bottled and river) and beverage (cola and green tea)

Magnetic graphene

MSPE HPLC-UV/vis 80.0-106.0

0.01-0.04 ng mL-1

EF, 1574-2880

[17]

Triazine herbicides Water (reservoir, river and lake)

Magnetic graphene

MSPE HPLC-DAD

89.0-96.2

0.025-0.040 ng mL-1

EF, 247-295

[18]

Carbamate pesticides

Water (reservoir, river and pool)

Magnetic graphene

MSPE HPLC-DAD

87.0-97.3

0.02-0.04 ng mL-1

EF, 474-868

[19]

Page 51 of 63

Accep

ted

Man

uscr

ipt

49

Triazole fungicides Water (reservoir, river and sea)

Magnetic graphene

MSPE HPLC-UV

86.0-102.0

0.005-0.01 ng mL-1

EF, 3600-5824

[20]

Neonicotinoid insecticides

Water (reservoir, river and sea)

Magnetic graphene

MSPE HPLC-UV

86-110 0.004-0.01 ng mL-1

EF, 3325-4644 [21]

Active compounds from TCM and nicotine metabolites

Aqueous solutions Fe3O4@SiO2@Graphene

MSPE

MALDI-TOF MS

—

—

[22]

Sulfonamide antibiotics

Water (reservoir, sewage and waste)

Magnetic graphene

MSPE HPLC-UV

74.2-104.1

0.09-0.16 ng mL-1

[23]

Protein, peptide and lysozyme

Saliva samples

Fe3O4@SiO2@Graphene

MSPE

MALDI-TOF MS

58.2-101.2 3.8-68 fmol

[24]

Perfluoroalkyl and polyfluoroalkyl substances, alkylphenols and alkyltrimethylammonium salts

Water (river and sewage)

Hemimicelles/admicelles/ graphene

MSPE

HPLC-ESI-MS/MS, HPLC-UV

56.3-93.9

0.15-8.0 ng L-1

[25]

Active compounds from TCM, nicotine metabolites, carbohydrate, amino

acid and fatty acids

Urine samples

Magnetic graphene/CNTs

MSPE MALDI-TOF MS

—

—

[26]

Pyrethroid pesticides

Pond water

Graphene

SPME

GC-ECD

83-110

3.69-69.4 ng L-1

Immobilized on a stainless steel wire

[29]

Page 52 of 63

Accep

ted

Man

uscr

ipt

50

Carbamate pesticides

Water (tap, sea and lake)

Graphene

SPME

HPLC-DAD

83.8-95.4

0.1-0.8 ng mL-1

Immobilized on a stainless steel wire

[30]

Triazine herbicides Water (tap, sea and lake)

Graphene

SPME

HPLC-DAD

86.0-94.6

0.05-0.2 ng mL-1

Immobilized on a stainless steel wire

[31]

Organochlorine pesticides

Water (river) Graphene oxide HS-SPME

GC-ECD

80.1-101.1

0.16-0.93 ng L-1

Immobilized on a stainless steel wire with silicone glue

[32]

Phenols Pond water Polypyrrole/graphene

SPME

GC-FID

74.1-103.9

0.34-3.4 μg L-1

Immobilized on stainless steel wire

[33]

Ultraviolet filters River Water Graphene SPME GC-MS 99-114 0.5-6.8 ng L-1

Immobilized on a stainless steel plunger-in-needle; EF, 1080-10155

[34]

Polybrominated diphenyl ethers

Canal water

Graphene SPME GC-MS 74.8-81.9 0.2-5.3 ng L-1

Immobilized on a stainless steel plunger-in-needle; EF, 1378-2859

[35]

Sulfur volatiles Allium species Graphene/ZnO SPME GC-MS 73.2-80.6 0.1-0.7 μg L-1

Immobilized on a silica fiber

[36]

Polycyclic aromatic hydrocarbons

Water (river and running)

Graphene

SPME

GC-FID

84.5-118.2

5-80 ng L-1

Immobilized on a silica fiber with APTES

[37]

Polycyclic aromatic hydrocarbons

Water (river and pond) and soil

Graphene HS-SPME

GC-MS

72-102 1.52-2.72 ng L-1

Immobilized on a fused silica fiber with APTES; EF, >6300

[38]

Page 53 of 63

Accep

ted

Man

uscr

ipt

51

Amino acids, polyamine, nucleosides, cholesterol and squalene

Aqueous solutions, anticancer drugs

Graphene —

MALDI-TOF MS

—

—

Separation by centrifugation; graphene as LDI

[39]

Polycyclic aromatic hydrocarbons

River water Graphene —

MALDI-TOF MS

—

10-7 M for coronene

Separation by centrifugation; graphene as LDI

[40]

Ferulic acid, wogonin and scutellarin

Traditional Chinese medicine herbs

Graphene (G) or graphene oxide (GO)

—

MALDI-TOF MS

—

1-15 nM with G; 5-45 nM with GO

Separation by centrifugation; graphene as LDI

[41]

Long-chain fatty acids

Serum or urine

Graphene or graphene oxide

—

MALDI-TOF MS

85.4-122.6 74-715 fM with G; 16-380 fM with GO

Separation by centrifugation; graphene as LDI

[42]

Tetracycline

Milk Graphene or graphene oxide

—

MALDI-TOF MS

—

2-2.5 nM with GO; 10-15nM with G

Separation by centrifugation; graphene as LDI

[43]

DNA Oligomer

A mixture of Cyt C protein and DNA

Graphene or graphene oxide

—

SALDI-MS

—

100 fM for

ssDNA with

G; 1 fM with

GO and 1 pM

with G for Cyt

C

Separation by centrifugation; graphene as LDI

[44]

Page 54 of 63

Accep

ted

Man

uscr

ipt

52

Phosphopeptides

Cancer Cells

TiO2/graphene

—

SALDI-MS

—

5 attomol

Separation by centrifugation; graphene as LDI

[45]

Cocaine and adenosine

Plasma samples

Aptamer-Conjugated Graphene Oxide

—

MALDI-TOF MS

—

—

Separation by centrifugation; graphene as LDI

[46]

Polycyclic aromatic hydrocarbons

River water

Sulfonated graphene

μSPE GC-MS

81.6-113.5 0.8-3.9 ng L-1

Enclosed within a polypropylene membrane sheet envelope

[47]

Glucocorticoids Cosmetic products Graphene PMME LC-MS 83.7-103.8 0.13-1.93 ng mL-1

[48]

Polycyclic aromatic hydrocarbons

Tap and lake water

Graphene polymer composite

SRSE GC-MS Average 85.7

0.005-0.429 ng mL-1

[49]

PBDEs, methoxylated and hydroxylated analogs

Soil, treebark and fish

Graphene MSDP GC-ECD; LC-ESI-MS/MS

51.5-125.9 5.3–212.6 pg g-1

[50]

Phosphopeptides

Peptide mixtures

TiO2/graphene

—

MALDI-TOF MS

—

—

Separation by centrifugation

[51]

Low-abundance peptides

Mouse brain tissue

graphene@SiO2

@poly(methyl methacrylate)

—

MALDI-TOF MS

—

—

Separation by centrifugation

[52]

Endogenous peptides

Mouse brain tissue

C8-modified

graphene@mSiO2

—

MALDI-TOF MS

—

—

Separation by centrifugation

[53]

Page 55 of 63

Accep

ted

Man

uscr

ipt

53

Hemoglobin

Human whole blood

Graphene Oxide/SiO2

—

SDS-PAGE

—

—

Separation by centrifugation

[54]

Page 56 of 63

Accep

ted

Man

uscr

ipt

54

Table 2 Application of carbon nanofibers, nanocones/disks and nanohorns in sample preparation

Analyte Matrix Sorbent type Sample preparation

Techniques Recovery (%)

LODs Remarks References

Chlorotriazine, and dealkylated metabolites

Crude soil, water (tap, well and creek)

Carbon nanofibers

μSPE

LC-DAD 83.5-105.0

0.004-0.03 ng mL-1

Sequential injection assembly; EF, 20

[72]

Mn, Co and Ni Tap water, human hair and mussel

Carbon nanofibers

SPE ICP–MS

95-114

40,0.4 and 8.0 pg mL-1

Packing in minicolumn; EF, 150

[73]

Au and Pt

Geological Samples

Carbon nanofibers

SPE ICP–MS

95 0.15 and 0.02 ng mL-1

Packing in minicolumn; EF, 100

[74]

La, Ce, Sm, Eu, Dy and Y

Human hair

Carbon nanofibers

SPE ICP–MS

95-115

0.2-1.2 pg mL-1

Packing in minicolumn; EF, 100

[75]

La, Eu, Gd and Yb

Tea leaves and mussel

Carbon nanofibers

SPE ICP–MS

96-104

0.36-0.6 pg mL-1

Packing in minicolumn; EF, 100

[76]

Mn(II) and Mn(VII)

Groundwater, beef liver and mussel

Carbon nanofibers

SPE ICP–MS

93-103

0.04 and 0.048 ng mL-1

Packing in minicolumn; EF, 50

[77]

Cr(III) and Cr(VI)

Groundwater, tea leaves and mussel

Carbon nanofibers

SPE ICP–MS

97-104

0.015-0.033 ng mL-1

Packing in minicolumn; EF, 100

[78]

As(III) and As(V)

Water (certified, ground and lake)

Carbon nanofibers

SPE ICP–MS

92-106

0.0045 and 0.24 ng mL-1

Packing in minicolumn; EF, 33

[79]

BTEX and phenols Aqueous solutions Electrospun nanofibers

SPME

GC-FID

—

0.1-10 ng mL-1

Electrospinning onto a stainless steel wire

[81]

β-blockers Aqueous solutions Electrospun nanofibers

SPME

LC-UV/vis —

1 ng mL-1

Electrospinning onto a stainless steel wire

[82]

Page 57 of 63

Accep

ted

Man

uscr

ipt

55

Anilines Wastewater

Carbon nanofibers from soot

μSPE HPLC-UV/vis

70-108

0.009-0.081 μg L-1

[83]

Chlorophenols

Water (drinking, swimming pool, tank and well)

Carbon nanocones/disks

SPE GC-MS 98.8-100.9

0.3-8 ng mL-1

Packing in cartridge; EF, 40

[86]

BTEX

Water(tap, river and well)

Carbon nanocones/disks

SPME GC-MS 76-104 0.15-5 ng mL-1

Immobilized on a stainless steel needle by an organic binder

[88]

Polycyclic aromatic hydrocarbons

Water(tap, river and bottled mineral)

Oxidized carbon nanohorns

Dispersive SPME

GC-MS 74-83

30-60 ng L-1

Concentration of SWNHs, 0.2 mg L-1

[92]

Triazines

Water(tap, river and bottled mineral)

Oxidized carbon nanohorns

Dispersive SPME

GC-MS 87-94 15-100 ng L-1 Concentration of SWNHs, 0.2 mg L-1

[93]

4-nitrophenol

Water (lake)

Single-walled carbon nanohorn

SPE

Linear sweep voltammetry

92-106

11 nM

SWCNH-modified GCE.

[94]

Page 58 of 63

Accep

ted

Man

uscr

ipt

56

Table 3 Application of fullerenes in sample preparation Analyte Matrix Sorbent type Sample

preparation Techniques Recovery

(%) LODs Remarks References

Lead Aqueous solutions C60 On-line SPE

AAS

—

5 ng mL-1

Packing in minicolumn; EF, 70

[97]

Lead species Rainwater C60-NaDDC SPE GC-MS 92-100

4-15 ng L-1 Packing in minicolumn

[98]

Copper

Aqueous solutions C60, C70 On-line SPE

AAS

—

0.3 ng mL-1 Packing in minicolumn; EF, 40-185

[99]

Cadmium

Water, oyster tissue, pig kidney and bovine liver

C60 On-line SPE

AAS

—

0.3 ng mL-1 Packing in minicolumn; EF, 110

[100]

Cadmium, lead and nickel

Tap and sea waters

C60 On-line SPE

AAS

85-104

2.2-75 ng L-1

Packing in minicolumn; EF, 100-150

[101]

Cobalt Wheat flour C60 On-line SPE

AAS —

8 ng mL-1 Packing in minicolumn; EF, 40

[102]

Mercury(II), methylmercury(I) and ethylmercury(I)

Sea, waste and river waters

C60 SPE GC-MS 80-105

1.5 ng L-1 Packing in minicolumn

[103]

Organometallic compounds

Aqueous solutions C60 SPE GC-AAS —

5-15 ng mL-1

Packing in minicolumn; EF, 20-50

[104]

Cadmium and cadmium

Fish liver

C60 On-line SPE

FAAS 93-98 0.1 ng mL-1 Packing in minicolumn

[105]

Page 59 of 63

Accep

ted

Man

uscr

ipt

57

metallothioneins Metal dithiocarbamates

Grain samples C60 On-line SPE

FAAS 92-98 1-5 ng mL-1 Packing in minicolumn; EF, 45

[106]

Inorganic lead and trialkyllead compounds

Aqueous solutions

C60 On-line SPE

FAAS

—

1-4 ng mL-1

Packing in minicolumn

[107]

Inorganic lead and ionic alkyllead compounds

Rainwater

C60 SPE GC-MS or FAAS

—

1-4 ng mL-1 Packing in minicolumn

[108]

Butyltin compounds

Marine sediments

C60 SPE GC-MS

80-95 0.07-0.10 ng g-1

Packing in minicolumn

[109]

Mercury and tin compounds

Water and sediments

C60 SPE GC-MS 75-105 0.8-1.5 pg mL-1

Packing in minicolumn

[110]

BTEX Sea, waste, ground, rain, lake, drinking and river waters

C60 SPE GC-MS

94-104 0.04-0.05 μg L-1

Packing in minicolumn

[111]

Aromatic and non-aromatic N-nitrosamines

Swimming, waste, well, drinking and river waters

C60, C70 SPE GC-MS 95-102 4-15 ng L-1

Packing in minicolumn

[112]

Copper

Aqueous solutions

C60-rubeanic acid On-line SPE

FAAS

95.0-107.5

0.15 ng mL-1

Packing in minicolumn

[113]

V

Sea water, nutritional and biological substrates.

N-phenyl-(1,2 methanofullerene C60)61-formohydroxamic acid

LLE

ICP-AES

99.8

0.6 pg mL-1

EF, 108 [114]

Page 60 of 63

Accep

ted

Man

uscr

ipt

58

La and Ce

Real and standard samples, seawater, and environmental samples

N-phenyl-(1,2 methanofullerene C60)61-formohydroxamic acid

LLE

ICP-AES

99.98-99.99

0.5 ng mL-1

[115]

U

Serum, natural water, seawater, standard samples and monazite sand

N-phenyl-(1,2 methanofullerene C60)61-formohydroxamic acid

SFE

ICP-MS 99.99

0.005 ng mL-1

EF, 135 [116]

Lanthanides

Rocks, monazite sand and seawater

Poly(β-Styryl)-(1,2-Methanofullerene-C60)-61-Formo Hydroxamic Acid

SPE

ICP-MS

98.9-100.4

0.9-3.5 pg mL-1

Packing in a glass column

[117]

BTEX, naphthalene congeners, and phthalic acid diesters

Aqueous solutions

C60 HS-SPME GC-FID

—

0.00033-12.5 μg L-1

Immobilized on a fused-silica fiber

[118]

BTEX, naphthalene congeners and PAHs

Aqueous solutions

Polysilicone fullerene

HS-SPME GC-FID

—

0.04-2.21 μg L-1

Immobilized on a fused-silica fiber

[119]

PCBs, PAHs & polar aromatic amines

Sediment and waste water

Hydroxyfullerene

HS-SPME GC-FID; GC-ECD

87.1-103.6

0.0049-51 ng mL-1

Immobilized on a fused-silica fiber

[120]

Peptides and proteins

Aqueous solutions

C60-bound Silica SPE MALDI-TOF MS

72.3-99.7 —

Separation by centrifugation;

[121]

Tryptic peptides Aqueous solutions

C60-bound Silica SPE MALDI-TOF MS

86.3-94.7

—

Packing in cartridge [122]

Page 61 of 63

Accep

ted

Man

uscr

ipt

59

HPLC-UV/vis Amadori peptides

Human serum

C60-bound Silica SPE MALDI-TOF MS

— — [123]

Low-mass serum constituents

Serum

Fullerene derivatives

SPE MALDI-TOF MS

— —

[124]

Peptides and proteins

Urine C60-functionalized magnetic silica

MSPE MALDI-TOF MS

—

—

[125]

Surfactants, amino acids, peptides and proteins

Goat milk

Hexa(sulfonbutyl)fullerene

Ion-pair

precipitation

MALDI-TOF MS

—

—

Separation by centrifugation;

[126]

N-terminal sulfonated peptides

Aqueous solutions

C60-N,N-dimethylpyr

rolidinium iodide

Ion-pair

precipitation

ESI-IT MS —

—

Separation by centrifugation;

[127]

Page 62 of 63

Accep

ted

Man

uscr

ipt

60

Table 4 Comparison of carbon-based nanomaterials in sample preparation Materials Characteristics from others Derivatization methods Sample preparation Current status* Perspective* Graphene 1. Both available sides for adsorption;

2. Easily synthesized in lab 3. Easily modified with functional

groups

Modified via graphene oxide SPE; MSPE; SPME; LDI substrate; μSPE; PMME; MSDP; SRSE

★★★★★ ★★★★★

Carbon nanotubes** 1. Mostly used carbon nanomaterials 2. be easily covalently or

non-covalently functionalized

Oxidized CNTs can be grafted via creation of amide bonds, N2-plasma and radical addition

SPE; MSPE; SPME; LDI substrate; μSPE；SRSE

★★★★★ ★★★★★

Carbon nanofibers 1. Easily available on a large scale; 2. Larger dimensions without coating

or functionalization

Polar groups can be introduced by treating with the concentrated nitric acid

SPE; SPME; On-line μSPE

★★★ ★★★★

Fullerenes Firstly used carbon nanomaterials Covalently bonded to other reagents

SPE; On-line SPE; MSPE; SPME; LLE; SFE; Ion-pair precipitation

★★★★ ★

Nanodiamonds 1. Chemical inertness and hardness 2. More expensive than others

Functionalized with H/D-terminated, halogenated, aminated, hydroxylated, and carboxylated surfaces

SPE; LDI substrate ★★★ ★★★

Carbon nanocones, disks and nanohorns

1. Multiple structures; 2. Lower aggregation tendency

Functionalized by microwave (for SWNHs)

SPE; SPME ★★ ★★

* The star number represents the research status and perspective which is mainly based on properties of materials, the number of published articles and publication year. (It reflects the personal view of the authors);

** The information about sample preparation techniques is not comprehensive enough.

Page 63 of 63

Accep

ted

Man

uscr

ipt

Author Biography

Dr. Bo-Tao Zhang received his Ph.D. in Environmental Analytical

Chemistry under the supervision of Dr. Jin-Ming Lin from the Chinese

Academic of Sciences in 2008. From 2009 to 2010, he was a

postdoctoral fellow at University of Wyoming and Georgia Institute of

Technology. In 2011, he joined the faculty at College of Water

Sciences, Beijing Normal University. Currently, Dr. Zhang’s research

interests include new materials’ application in analytical chemistry and

free radicals’ application in advanced oxidation processes.

Xiaoxia Zheng graduated from Nankai University in 2010. She is a

joint Master candidate in Tsinghua University and Beijing Normal

University now. Her interests include the development of pretreatment

methods and materials in complicated environmental samples.

Dr. Hai-Fang Li is a senior engineer specialist for organic mass

spectrometers in the Department of Chemistry at Tsinghua University.

She took her postdoctoral research from 2005-2007 and now still work

as a research assistant in the Biochemical and Environmental Lab in

Tsinghua University. She received her Ph.D. degree in the Research

Center for Eco-Environmental Sciences, Chinese Academy of Sciences

in 2005. She is the author and co-author of 52 research papers

published in international journals. Her current research is focused on

trace analysis based on microfluidic devices, sample pretreatment and

chromatography /mass spectrometry analysis.

Professor Dr. Jin-Ming Lin received his BA degree in 1984 and PhD

at Tokyo Metropolitan University in 1997. He had studied and worked

in Showa University and Tokyo Metropolitan University during

1992-2002. He is currently a professor of Tsinghua University and a

Deputy General-in-Secretary of Chinese Chemical Society, a member

of council of Chinese Society for Chromatography Science. He service

as associate Editor or Editorial Board for seven international journals.

He received more 20 awards for his contributions in

chemiluminescence and separation science. His current research is

focused on sample pretreatment, chemiluminescence and microfluidic

device. He is the author and co-author of 278 original research papers

published in international journals, 28 reviews, 4 books and 35 patents.

*Author Biography (one per author)