Progress in application of functionalized magnetic nanomaterials for sample pretreatment

doi:10.3724/SP.J.1123.2019.06034

Abstract

Abstract:

With the increasing complexity of the sample properties in analytical chemistry and the lower concentrations of the detected substances, it is imperative to develop accurate and efficient sample pretreatment processes before chromatography and mass spectrometry analyses. Magnetic solid-phase extraction (MSPE) can be regarded as an efficient sample pretreatment method due to the simple synthesis, convenient operation, and high extraction efficiency. In recent years, Fe₃O₄ magnetic nanomaterials have been widely used in separation and analysis due to their advantages such as high separation speed, good dispersion, and biocompatibility. Functionalized Fe₃O₄ magnetic nanomaterials are expected to show greatly improved physical and chemical stability, with superior adsorption and separation ability. In this paper, the preparation of magnetic nanomaterials functionalized with carbon-based nanomaterials, molecularly imprinted polymers, ionic liquids, boronate affinity ligands, metal organic frameworks, covalent organic frames, quantum dots, and metal oxides and their applications to sample pretreatment in the fields of biological, environmental, and food safety are reviewed. In addition, future research on sample pretreatment processes is prospected.

Key words: magnetic nanomaterials, functionalization, sample pretreatment, review

LI Fei, WU Haocheng, LI Yijun, HE Xiwen, CHEN Langxing, ZHANG Yukui. Progress in application of functionalized magnetic nanomaterials for sample pretreatment[J]. Chinese Journal of Chromatography, 2020, 38(1): 2-13.

Figures/Tables 8

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Matrix	Sample	Analyte	Analytical technique	Reference
MCNTs: magnetic carbon nanotubes; MGO: magnetic graphene oxide; MC₃N₄: magnetic graphitic carbon nitride (g-C₃N₄); BHb: bovine hemoglobin; BSA: bovine serum albumin; AAS: atomic absorption spectroscopy; HRMS: high resolution mass spectrometry; UHPLC: ultra high performance liquid chromatography; FAAS: flame atomic absorption spectrometry; CVAFS: chemical vapor atomic fluorescence spectroscopy; ICP: inductive coupled plasma emission spectrometry.
MCNTs	human samples	sunitinib	HPLC	[21]
	wastewater	atrazine	HPLC-UV	[22]
		Cu²⁺	AAS
	traditional Chinese medicine	lappaconite, benzoylmesaconine	HPLC	[34]
	human blood	BHb, BSA	UV-Vis	[35]
	milk	sulfonamides	LC-HRMS	[36, 37]
	honey		HPLC
	fruit juice	patulin	HPLC	[38]
	synthetic urine	2-aminothiazoline-4-carboxylic acid	GC-MS	[39]
	bovine blood
	wastewater	methyl orange chromium (Ⅵ)	UV-Vis	[40]
	environmental water	sulfonamide antibiotics	UHPLC-MS/MS	[41, 42]
		pesticides	GC-MS
	urine, blood serum, opium, et al	codeine morphine	HPLC	[43]
MGO	wastewater	chlorpheniramine	GC-MS	[44, 45]
	human plasma		HPLC-UV
	water	Zn (Ⅱ)	FAAS	[46]
	food samples
	human plasma	duloxetine	HPLC-UV	[47]
	wastewater	Cr (Ⅵ)	UV-Vis	[48]
	wastewater	Cd (Ⅱ)	AAS	[49]
		ionic dyes
MC₃N₄	wastewater	Hg (Ⅱ)	CVAFS	[33]
	industrial soil sludge samples	Cr (Ⅵ)	ICP-MS	[50]
	chicken eggs	fluoroquinolones	HPLC-UV	[51]
	wastewater	Cd (Ⅱ), Pb (Ⅱ), Zn (Ⅱ)	ICP-MS	[52]
	wastewater	polycyclic aromatic hydrocarbons	GC, HPLC	[53, 54]
	wastewater	Pb (Ⅱ)	ICP-MS	[55]
	urine	hydroxyl polycyclic aromatic hydrocarbons	HPLC	[56]

Matrix	Sample	Analyte	Analytical technique	Reference
MCNTs: magnetic carbon nanotubes; MGO: magnetic graphene oxide; MC₃N₄: magnetic graphitic carbon nitride (g-C₃N₄); BHb: bovine hemoglobin; BSA: bovine serum albumin; AAS: atomic absorption spectroscopy; HRMS: high resolution mass spectrometry; UHPLC: ultra high performance liquid chromatography; FAAS: flame atomic absorption spectrometry; CVAFS: chemical vapor atomic fluorescence spectroscopy; ICP: inductive coupled plasma emission spectrometry.
MCNTs	human samples	sunitinib	HPLC	[21]
	wastewater	atrazine	HPLC-UV	[22]
		Cu²⁺	AAS
	traditional Chinese medicine	lappaconite, benzoylmesaconine	HPLC	[34]
	human blood	BHb, BSA	UV-Vis	[35]
	milk	sulfonamides	LC-HRMS	[36, 37]
	honey		HPLC
	fruit juice	patulin	HPLC	[38]
	synthetic urine	2-aminothiazoline-4-carboxylic acid	GC-MS	[39]
	bovine blood
	wastewater	methyl orange chromium (Ⅵ)	UV-Vis	[40]
	environmental water	sulfonamide antibiotics	UHPLC-MS/MS	[41, 42]
		pesticides	GC-MS
	urine, blood serum, opium, et al	codeine morphine	HPLC	[43]
MGO	wastewater	chlorpheniramine	GC-MS	[44, 45]
	human plasma		HPLC-UV
	water	Zn (Ⅱ)	FAAS	[46]
	food samples
	human plasma	duloxetine	HPLC-UV	[47]
	wastewater	Cr (Ⅵ)	UV-Vis	[48]
	wastewater	Cd (Ⅱ)	AAS	[49]
		ionic dyes
MC₃N₄	wastewater	Hg (Ⅱ)	CVAFS	[33]
	industrial soil sludge samples	Cr (Ⅵ)	ICP-MS	[50]
	chicken eggs	fluoroquinolones	HPLC-UV	[51]
	wastewater	Cd (Ⅱ), Pb (Ⅱ), Zn (Ⅱ)	ICP-MS	[52]
	wastewater	polycyclic aromatic hydrocarbons	GC, HPLC	[53, 54]
	wastewater	Pb (Ⅱ)	ICP-MS	[55]
	urine	hydroxyl polycyclic aromatic hydrocarbons	HPLC	[56]

Sample	Analyte	Analytical technique	Reference
RLS: resonance light scattering.
Human serum	atropine	GC-MS	[61]
Human serum	transferrin	fluorescence spectrophotometer	[63]
Porcine blood serum real sample	porcine serum albumin	HPLC	[64]
Real plasma	buprenorphine	HPLC-UV	[65]
Urine samples tablets
River water	fluoroquinolones	HPLC	[66]
Flooded soil water, paddy soil	herbicide diuron		[67]
Grain seedlings		HPLC
Calf blood	bovine hemoglobin	UV-Vis	[68, 69]
Bovine blood		HPLC
Human serum	hepatitis A virus	RLS	[70]
Rice and wine	ochratoxins	HPLC	[71]
Apple	imidacloprid	HPLC	[72]
Rhododendron species	flavonoids	LC-MS/MS	[73]
Apple	quercetin	HPLC	[74]
Weight-loss products	sibutramine	HPLC-MS	[75]
Water samples	microcystin-LR	HPLC	[76]
Water samples	phthalates esters	GC/MS	[77]
Rat urine	aristolochic acid I and II	HPLC	[78]
Natural medical plants	sibiskoside	HPLC	[79]
Herb extract	hypericin	HPLC	[80]
Human milk	vitamin B₁₂	UV spectrophotometer	[81]
Azo dyes	aromatic amines	UV-Vis	[82]
Edible oil	phthalate plasticizers	GC	[83]
Human plasma	6-mercaptopurine thioguanine	LC-MS/MS	[84]
Pine cone	polysaccharide	HPLC	[85]

Sample	Analyte	Analytical technique	Reference
RLS: resonance light scattering.
Human serum	atropine	GC-MS	[61]
Human serum	transferrin	fluorescence spectrophotometer	[63]
Porcine blood serum real sample	porcine serum albumin	HPLC	[64]
Real plasma	buprenorphine	HPLC-UV	[65]
Urine samples tablets
River water	fluoroquinolones	HPLC	[66]
Flooded soil water, paddy soil	herbicide diuron		[67]
Grain seedlings		HPLC
Calf blood	bovine hemoglobin	UV-Vis	[68, 69]
Bovine blood		HPLC
Human serum	hepatitis A virus	RLS	[70]
Rice and wine	ochratoxins	HPLC	[71]
Apple	imidacloprid	HPLC	[72]
Rhododendron species	flavonoids	LC-MS/MS	[73]
Apple	quercetin	HPLC	[74]
Weight-loss products	sibutramine	HPLC-MS	[75]
Water samples	microcystin-LR	HPLC	[76]
Water samples	phthalates esters	GC/MS	[77]
Rat urine	aristolochic acid I and II	HPLC	[78]
Natural medical plants	sibiskoside	HPLC	[79]
Herb extract	hypericin	HPLC	[80]
Human milk	vitamin B₁₂	UV spectrophotometer	[81]
Azo dyes	aromatic amines	UV-Vis	[82]
Edible oil	phthalate plasticizers	GC	[83]
Human plasma	6-mercaptopurine thioguanine	LC-MS/MS	[84]
Pine cone	polysaccharide	HPLC	[85]

Sample	Analyte	Analytical technique	Reference
PAHs: polycyclic aromatic hydrocarbons; CAP: chloramphenicol; ETAAS: electrothermal atomic absorption spectrometry; TD: thermal desorption.
Vegetables	preservatives	UPLC-MS/MS	[102]
Honey samples	As (Ⅲ)	ETAAS	[103]
Water samples, including tap, lake and pool water	UV filters,	HPLC	[104]
	PAHs, alkylphenols,
	a plasticizer
	a preservative
Rice samples	PAHs	GC-FID	[105]
Vegetables and fruits	pesticides	HPLC	[106]
Vegetables	preservatives bearing phenyl moieties	UPLC-MS/MS	[107]
Human urine	estrogens	HPLC	[108]
Water samples	chlorobenzenes	TD-GC-MS	[109]
Water samples	PAHs	TD-GC-MS	[110]
Environmental water samples	CAP	HPLC	[111]