March 2021 Ｖｏｌ．３９ Ｎｏ．３

Ｍａｒｃｈ ２０２１ Ｃｈｉｎｅｓｅ Ｊｏｕｒｎａｌ ｏｆ Ｃｈｒｏｍａｔｏｇｒａｐｈｙ ２２９～２４０

ＤＯＩ： １０．３７２４ ／ＳＰ．Ｊ．１１２３．２０２０．０５０３

Monographs and ０
overviews

Construction of solid columns of nanomaterials adulterated

polymers and their application in the area of pretreatment
Li Ziling, Li Na, Zhao Tengwen, Zhang Ziyang, Wang Manman*
(North China University of Technology Public Health College, Tangshan, Hebei Province 0 6320)

Summary: A polymer monolith is a rod-shaped monomer, crosslinking agent, initiator, and tracer
that is aggregated in situ in the mold. Compared to traditional filled solid phase extraction
columns, polymer monolith adsorbents have been widely used in pretreatment in food analysis,
biomedical and environmental hygiene, thanks to the advantages of simple preparation, low column
pressure, fast transfer and wide use of the PH. However, often due to the difficult-to-control
aggregation method, polymer monolith columns are prone to particle accumulation during
preparation, uneven well passages, resulting in low porosity and limited surface area. In recent
years, new adsorbers that doped nanomaterials to polymer monolith columns for orderly structural
distribution, good absorption efficiency, and superior selective performance have become research
hot spots. Nanomaterials are diverse in variety and small in size, taking advantage of their
rich surface active subgroups, action sites, and very large scale area, and so on, using simple
adulteration, Synthesis of nanodoped polymer monolith columns by methods such as co-aggregation
and in situ modification not only improves its micro structure, mechanical strength and stability
of the column bed, but also significantly improves the extraction performance and selectivity of
doped polymer monolith adsorbents. The article provides an overview of polymer monolders
adulterated by different nanomaterials such as carbon materials, metals and metal oxides, metal
organic skeletons, covalent organic skeletons, and inorganic nanoparticles, common construction
methods, and the extraction of such sorbents in solid phases. Applications in the areas of pre-
sample processing such as solid phase micro-extraction, agitation bar adsorption extraction and
online solid phase extraction, and looking forward to the development trends and application
prospects of this research, with a view to providing reference for pre-processing research.
Keywords: Nanomaterials; Polymer monolith; Pre-sample processing; Overview
Middle view Classification number : O658 Literature ID: A. Article number: 1,000 8713 (2021) 03 829 twelve

Ｆａｂｒｉｃａｔｉｏｎ ｏｆ ｎａｎｏｍａｔｅｒｉａｌｓ ｉｎｃｏｒｐｏｒａｔｅｄ ｐｏｌｙｍｅｒｉｃ

ｍｏｎｏｌｉｔｈｓ ａｎｄ ａｐｐｌｉｃａｔｉｏｎ ｉｎ ｓａｍｐｌｅ ｐｒｅｔｒｅａｔｍｅｎｔ
ＬＩ Ｚｉｌｉｎｇ， ＬＩ Ｎａ， ＺＨＡＯ Ｔｅｎｇｗｅｎ， ＺＨＡＮＧ Ｚｉｙａｎｇ， ＷＡＮＧ Ｍａｎｍａｎ ∗
（Ｓｃｈｏｏｌ ｏｆ Ｐｕｂｌｉｃ Ｈｅａｌｔｈ， Ｎｏｒｔｈ Ｃｈｉｎａ Ｕｎｉｖｅｒｓｉｔｙ ｏｆ Ｓｃｉｅｎｃｅ ａｎｄ Ｔｅｃｈｎｏｌｏｇｙ， Ｔａｎｇｓｈａｎ ０６３２１０， Ｃｈｉｎａ）

Ａｂｓｔｒａｃｔ： Ｐｏｌｙｍｅｒｉｃ ｍｏｎｏｌｉｔｈｉｃ ｃｏｌｕｍｎｓ ａｒｅ ｆａｂｒｉｃａｔｅｄ ｂｙ ｉｎ ｓｉｔｕ ｐｏｌｙｍｅｒｉｚａｔｉｏｎ ｏｆ ｔｈｅ ｃｏｒｒｅ⁃ｓｐｏ
ｎｄｉｎｇ ｍｏｎｏｍｅｒ， ｃｒｏｓｓｌｉｎｋｅｒｓ， ｐｏｒｏｇｅｎｉｃ ｓｏｌｖｅｎｔｓ ａｎｄ ｒａｄｉｃａｌ ｉｎｉｔｉａｔｏｒｓ ｗｉｔｈｉｎ ａ ｍｏｌｄ． Ｃｏｍ⁃ｐａ
ｒｅｄ ｗｉｔｈ ｔｈｅ ｃｏｎｖｅｎｔｉｏｎａｌ ｐａｃｋｅｄ ｓｏｌｉｄ ｐｈａｓｅ ｅｘｔｒａｃｔｉｏｎ ａｄｓｏｒｂｅｎｔｓ， ｐｏｌｙｍｅｒｉｃ ｍｏｎｏｌｉｔｈｉｃｃｏｌｕ
ｍｎｓ ｗｉｔｈ ａ ｃｏｎｔｉｎｕｏｕｓ ｐｏｒｏｕｓ ｓｔｒｕｃｔｕｒｅ ｐｒｏｃｅｓｓ ｄｉｓｔｉｎｃｔｉｖｅ ａｄｖａｎｔａｇｅｓ ｏｆ ｒａｐｉｄ ｍａｓｓ ｔｒａｎｓ⁃ｆｅｒ
ａｎｄ ｅｘｃｅｌｌｅｎｔ ｐｅｒｍｅａｂｉｌｉｔｙ， ｗｈｉｃｈ ｆａｃｉｌｉｔａｔｅｓ ｔｈｅ ｅｘｔｒａｃｔｉｏｎ ｏｆ ｔｒａｃｅ ａｍｏｕｎｔｓ ｏｆ ｔｈｅ ｔａｒｇｅｔｆｒｏｍ ｔｈ
ｅ ｍａｔｒｉｘ ｅｖｅｎ ａｔ ｈｉｇｈ ｆｌｏｗ ｖｅｌｏｃｉｔｉｅｓ． Ｂｅｓｉｄｅｓ， ｔｈｅｓｅ ｍａｔｅｒｉａｌｓ ｃａｎ ｂｅ ｅａｓｉｌｙ ｆａｂｒｉｃａｔｅｄ ｉｎｓｉｔｕ ｗｉ
ｔｈｉｎ ｖａｒｉｏｕｓ ｃａｒｔｒｉｄｇｅｓ， ａｖｏｉｄｉｎｇ ａ ｆｕｒｔｈｅｒ ｐａｃｋｉｎｇ ｓｔｅｐ ａｓｓｏｃｉａｔｅｄ ｗｉｔｈ ｐａｃｋｅｄ ｐａｒｔｉｃｕ⁃ｌａｔｅ ａｄｓ
ｏｒｂｅｎｔｓ． Ａｄｄｉｔｉｏｎａｌｌｙ， ｔｈｅ ａｂｕｎｄａｎｔ ｍｏｎｏｍｅｒ ａｖａｉｌａｂｉｌｉｔｙ， ｆｌｅｘｉｂｌｅ ｐｏｒｏｕｓ ｓｔｒｕｃｔｕｒｅ，ａｎｄ ｗｉｄｅ ａ
ｐｐｌｉｃａｂｌｅ ｐＨ ｒａｎｇｅ ｍａｋｅ ｍｏｎｏｌｉｔｈｓ ｖｅｒｓａｔｉｌｅ ｆｏｒ ｕｓｅ ｉｎ ｓｅｐａｒａｔｉｏｎ ｓｃｉｅｎｃｅ． Ｔｈｕｓ， ｐｏｌ⁃ｙｍｅｒｉｃ ｍ
 ｏｎｏｌｉｔｈｉｃ ｃｏｌｕｍｎｓ ｈａｖｅ ｂｅｅｎ ｉｎｃｒｅａｓｉｎｇｌｙ ａｐｐｌｉｅｄ ａｓ ｅｆｆｉｃｉｅｎｔ ａｎｄ ｐｒｏｍｉｓｉｎｇ ｅｘｔｒａｃｔｉｏｎｍｅｄｉａ ｆｏｒ
ｓａｍｐｌｅ ｐｒｅｔｒｅａｔｍｅｎｔ ｆｏｏｄ， ｐｈａｒｍａｃｅｕｔｉｃａｌ， ｂｉｏｌｏｇｉｃａｌ ａｎｄ ｅｎｖｉｒｏｎｍｅｎｔａｌ ａｎａｌｙｓｅｓ．Ｈｏｗｅｖｅｒ， ｔ
ｈｅｓｅ ｍａｔｅｒｉａｌｓ ｕｓｕａｌｌｙ ｈａｖｅ ｔｈｅ ｄｉｆｆｉｃｕｌｔｙ ｉｎ ｍｏｒｐｈｏｌｏｇｙ ｃｏｎｔｒｏｌ ａｎｄ ｔｈｅｉｒ ｉｎｔｅｒｃｏｎ⁃ｎｅｃｔｅｄ ｐｏｒｏｕｓ
ｍｉｃｒｏ⁃ｇｌｏｂｕｌａｒ ｓｔｒｕｃｔｕｒｅ， ｗｈｉｃｈ ｍａｙ ｒｅｓｕｌｔ ｉｎ ｌｏｗ ｐｏｒｏｓｉｔｙ， ｌｉｍｉｔｅｄ ｓｐｅｃｉｆｉｃ ｓｕｒ⁃ｆａｃｅ ａｒｅａ ａｎｄ ｐｏ
ｏｒ ｅｆｆｉｃｉｅｎｃｙ． Ｉｎ ａｄｄｉｔｉｏｎ， ｐｏｌｙｍｅｒｉｃ ｍｏｎｏｌｉｔｈｓ ｓｕｆｆｅｒ ｆｒｏｍ ｔｈｅ ｓｗｅｌｌｉｎｇ ｉｎｏｒｇａｎｉｃ ｓｏｌｖｅｎｔｓ， ｔｈｕｓ
ｄｅｃｒｅａｓｉｎｇ ｔｈｅ ｓｅｒｖｉｃｅ ｌｉｆｅ ａｎｄ ｐｒｅｃｉｓｉｏｎ ｗｈｉｌｅ ｉｎｃｒｅａｓｉｎｇ ｔｈｅ ｃｏｓｔ ｃｏｎ⁃ｓｕｍｐｔｉｏｎ． Ｒｅｃｅｎｔｌｙ， ｔｈｅ
ｄｅｖｅｌｏｐｍｅｎｔ ｏｆ ｎａｎｏｍａｔｅｒｉａｌ⁃ｉｎｃｏｒｐｏｒａｔｅｄ ｐｏｌｙｍｅｒｉｃ ｍｏｎｏｌｉｔｈｓ ｗｉｔｈ ａｎ
NNNN
Contact person. Ｅ⁃ｍａｉｌ： ｍｍｗａｎｇｈｅｕｕ＠１２６．ｃｏｍ．
Fund Project: Hebei Provincial Department of Education Key projects (ZD 2018014).
Ｆｏｕｎｄａｔｉｏｎ ｉｔｅｍ： Ｒｅｓｅａｒｃｈ Ｆｏｕｎｄａｔｉｏｎ ｏｆ Ｅｄｕｃａｔｉｏｎ Ｂｕｒｅａｕ ｏｆ Ｈｅｂｅｉ Ｐｒｏｖｉｎｃｅ （ Ｎｏ． ＺＤ２０１８０１４） ．
 ·２３０· Color Spectra Vol. 39

ｉｍｐｒｏｖｅｄ ｏｒｄｅｒｅｄ ｓｔｒｕｃｔｕｒｅ， ｅｎｈａｎｃｅｄ ａｄｓｏｒｐｔｉｏｎ ｅｆｆｉｃｉｅｎｃｙ ａｎｄ ｏｕｔｓｔａｎｄｉｎｇ ｓｅｌｅｃｔｉｖｉｔｙ ｈａ

ａｔｔｒａｃｔｅｄ ｃｏｎｓｉｄｅｒａｂｌｅ ａｔｔｅｎｔｉｏｎ． Ｎａｎｏｐａｒｔｉｃｌｅｓ ａｒｅ ｃｏｎｓｉｄｅｒｅｄ ａｓ ｐａｒｔｉｃｕｌａｔｅｓ ｗｉｔｈｉｎ ｔｈｅ ｓｉ
ｒａｎｇｅ ｏｆ １－１００ ｎｍ ｉｎ ａｔ ｌｅａｓｔ ｏｎｅ ｄｉｍｅｎｓｉｏｎ， ｗｈｉｃｈ ｅｎｄｏｗｓ ｔｈｅｍ ｗｉｔｈ ｕｎｉｑｕｅ ｏｐｔｉｃａｌ， ｅｌｅｃｔｒｉ⁃
ｃａｌ ａｎｄ ｍａｇｎｅｔｉｃ ｐｒｏｐｅｒｔｉｅｓ． Ｔｈｅｓｅ ｍａｔｅｒｉａｌｓ ｈａｖｅ ａ ｌａｒｇｅ ｓｕｒｆａｃｅ ａｒｅａ， ｅｘｃｅｌｌｅｎｔ ｔｈｅｒｍａｌ ａｎｄ
ｃｈｅｍｉｃａｌ ｓｔａｂｉｌｉｔｉｅｓ， ｒｅｍａｒｋａｂｌｅ ｖｅｒｓａｔｉｌｉｔｙ， ａｓ ｗｅｌｌ ａｓ ａ ｗｉｄｅ ｖａｒｉｅｔｙ ｏｆ ａｃｔｉｖｅ ｆｕｎｃｔｉｏｎａｌ ｇｒｏｕｐｓ
ｏｎ ｔｈｅｉｒ ｓｕｒｆａｃｅ． Ｗｉｔｈ ｔｈｅ ａｉｍ ｏｆ ｅｘｐｌｏｉｔｉｎｇ ｔｈｅｓｅ ａｄｖａｎｔａｇｅｓ， ｒｅｓｅａｒｃｈｅｒｓ ｈａｖｅ ｓｈｏｗｎ ｇｒｅ
ｉｎｔｅｒｅｓｔ ｉｎ ａｐｐｌｙｉｎｇ ｎａｎｏｍａｔｅｒｉａｌ⁃ｉｎｃｏｒｐｏｒａｔｅｄ ｐｏｌｙｍｅｒｉｃ ｍｏｎｏｌｉｔｈｓ ｔｏ ｓｅｐａｒａｔｉｏｎ ｓｃｉｅｎｃｅ．
Ａｃｃｏｒｄｉｎｇｌｙ， ｓｉｇｎｉｆｉｃａｎｔ ｐｒｏｇｒｅｓｓ ｈａｓ ｂｅｅｎ ａｃｈｉｅｖｅｄ ｉｎ ｔｈｉｓ ｆｉｅｌｄ． Ｎａｎｏｍａｔｅｒｉａｌｓ ｃａｎ ｂｅｅｎｔ
ｒａｐｐｅｄ ｖｉａ ｔｈｅ ｄｉｒｅｃｔ ｓｙｎｔｈｅｓｉｓ ｏｆ ａ ｐｏｌｙｍｅｒｉｚａｔｉｏｎ ｓｏｌｕｔｉｏｎ ｔｈａｔ ｃｏｎｔａｉｎｓ ｗｅｌｌ ｄｉｓｐｅｒｓｅｄ
ｎａｎｏｍａｔｅｒｉａｌｓ ｉｎ ｐｏｒｏｇｅｎｓ． Ｉｎ ａｄｄｉｔｉｏｎ， ｎａｎｏｐａｒｔｉｃｌｅｓ ｃａｎ ｂｅ ｉｎｃｏｒｐｏｒａｔｅｄ ｉｎｔｏ ｔｈｅ ｍｏｎｏｌｉｔｈ
ｍａｔｒｉｘ ｂｙ ｃｏｐｏｌｙｍｅｒｉｚａｔｉｏｎ ａｎｄ ｐｏｓｔ⁃ｐｏｌｙｍｅｒｉｚａｔｉｏｎ ｍｏｄｉｆｉｃａｔｉｏｎ ｖｉａ ｓｐｅｃｉｆｉｃ ｉｎｔｅｒａｃｔｉｏｎｓ
Ｔｈｅｒｅｆｏｒｅ， ｎａｎｏｍａｔｅｒｉａｌ⁃ｉｎｃｏｒｐｏｒａｔｅｄ ｐｏｌｙｍｅｒｉｃ ｍｏｎｏｌｉｔｈｓ ｃｏｍｂｉｎｅｄ ｔｈｅ ｄｉｆｆｅｒｅｎｔ ｓｈａｐｅｓ
ｃｈｅｍｉｃａｌ ｐｒｏｐｅｒｔｉｅｓ， ａｎｄ ｐｈｙｓｉｃａｌ ｐｒｏｐｅｒｔｉｅｓ ｏｆ ｔｈｅ ｐｏｌｙｍｅｒｓ ｗｉｔｈ ｔｈｏｓｅ ｏｆ ｔｈｅ ｎａｎｏｐａｒｔｉｃｌｅｓ．
Ｔｈｅ ｐｒｅｓｅｎｃｅ ｏｆ ｎａｎｏｐａｒｔｉｃｌｅｓ ｃａｎ ｉｍｐｒｏｖｅ ｔｈｅ ｓｔｒｕｃｔｕｒａｌ ｒｉｇｉｄｉｔｙ ａｓ ｗｅｌｌ ａｓ ｔｈｅ ｔｈｅｒｍａｌ ａｎｄ
ｃｈｅｍｉｃａｌ ｓｔａｂｉｌｉｔｉｅｓ ｏｆ ｍｏｎｏｌｉｔｈｉｃ ａｄｓｏｒｂｅｎｔｓ． Ｂｅｓｉｄｅｓ， ｎａｎｏｐａｒｔｉｃｌｅｓ ａｒｅ ｃａｐａｂｌｅ ｏｆ ｉｎｃｒｅａｓｉｎｇ
ｔｈｅ ｓｐｅｃｉｆｉｃ ｓｕｒｆａｃｅ ａｒｅａ ａｎｄ ｐｒｏｖｉｄｉｎｇ ｍｕｌｔｉｐｌｅ ａｃｔｉｖｅ ｓｉｔｅｓ， ｗｈｉｃｈ ｌｅａｄｓ ｔｏ ｅｎｈａｎｃｅｄ ｅｘｔｒａｃｔｉｏｎ
ｐｅｒｆｏｒｍａｎｃｅ ａｎｄ ｓｅｌｅｃｔｉｖｉｔｙ ｏｆ ｐｏｌｙｍｅｒｉｃ ｍｏｎｏｌｉｔｈｉｃ ｍａｔｅｒｉａｌｓ． Ｉｎ ｒｅｃｅｎｔ ｙｅａｒｓ， ｄｉｖｅｒｓｅ ｔｙｐｅｓ ｏｆ
ｎａｎｏｍａｔｅｒｉａｌｓ， ｓｕｃｈ ａｓ ｃａｒｂｏｎａｃｅｏｕｓ ｎａｎｏｐａｒｔｉｃｌｅｓ， ｍｅｔａｌｌｉｃ ｍａｔｅｒｉａｌｓ ａｎｄ ｍｅｔａｌ ｏｘｉｄｅｓ， ｍｅｔａｌ⁃
ｏｒｇａｎｉｃ ｆｒａｍｅｗｏｒｋｓ， ｃｏｖａｌｅｎｔ ｏｒｇａｎｉｃ ｆｒａｍｅｗｏｒｋｓ ａｎｄ ｉｎｏｒｇａｎｉｃ ｎａｎｏｐａｒｔｉｃｌｅｓ ｈａｖｅ ｂｅｅｎ ｅｘｔｅｎ⁃
ｓｉｖｅｌｙ ｅｘｐｌｏｒｅｄ ａｓ ｈｙｂｒｉｄ ａｄｓｏｒｂｅｎｔｓ ｉｎ ｔｈｅ ｍｏｄｅｓ ｏｆ ｓｏｌｉｄ ｐｈａｓｅ ｅｘｔｒａｃｔｉｏｎ， ｓｏｌｉｄ ｐｈａｓｅ ｍｉｃｒｏ⁃
ｅｘｔｒａｃｔｉｏｎ， ｓｔｉｒ ｂａｒ ｓｏｒｐｔｉｏｎ ｅｘｔｒａｃｔｉｏｎ ａｎｄ ｏｎ⁃ｌｉｎｅ ｓｏｌｉｄ ｐｈａｓｅ ｅｘｔｒａｃｔｉｏｎ． Ｔｈｉｓ ｒｅｖｉｅｗ ｓｐｅｃｉｆｉｃ⁃
ａｌｌｙ ｓｕｍｍａｒｉｚｅｓ ｔｈｅ ｆａｂｒｉｃａｔｉｏｎ ｍｅｔｈｏｄｓ ｆｏｒ ｎａｎｏｍａｔｅｒｉａｌ ｉｎｃｏｒｐｏｒａｔｅｄ ｐｏｌｙｍｅｒｉｃ ｍｏｎｏｌｉｔｈｓ ａｎｄ
ｔｈｅｉｒ ａｐｐｌｉｃａｔｉｏｎ ｔｏ ｔｈｅ ｆｉｅｌｄ ｏｆ ｓａｍｐｌｅ ｐｒｅｔｒｅａｔｍｅｎｔ． Ｔｈｅ ｅｘｉｓｔｉｎｇ ｃｈａｌｌｅｎｇｅｓ ａｎｄ ｆｕｔｕｒｅ ｐｏｓｓｉｂｌｅ
ｐｅｒｓｐｅｃｔｉｖｅｓ ｉｎ ｔｈｅ ｆｉｅｌｄ ａｒｅ ａｌｓｏ ｄｉｓｃｕｓｓｅｄ．

Ｋｅｙ ｗｏｒｄｓ： ｎａｎｏｍａｔｅｒｉａｌｓ； ｐｏｌｙｍｅｒｉｃ ｍｏｎｏｌｉｔｈｉｃ ｃｏｌｕｍｎｓ； ｓａｍｐｌｅ ｐｒｅｔｒｅａｔｍｅｎｔ； ｒｅｖｉｅｗ

This paper provides an overview of the
Polymer monolith was proposed by Hjértén et al. construction of nanomaterial adulterated
[1] in 1989. polymer monolith columns
It is passed through the mold by monomers,
crossers, triggers, and tracers And applications in pre-sample processing.
The aggregate of bits is a bar-shaped whole.
Unlike traditional fill columns, gather 1 nanomaterials doped polymer monolith
The compound column is simple and flexible,
with unique continuous knot
The structure gives it the advantages of good Nanomaterials are those in which at least one
permeability, low column pressure and fast mass dimension is nano-sized in three-dimensional
transfer, and, in addition, space
Organic polymer monolith biocompatibility is Meters (1～100nm) or materials made up of
good and the PH usage range is good nanometers as basic elements
Broad. Based on the above many advantages, Materials, and thus is bizarre in optics,
the polymer column is separated electromagnetics, magnetics, and chemistry
The analytical aspect is well received, The characteristics of the . Nanomaterials are
especially as an adsorbent material diverse and small in size, with a larger ratio
Widely used in the fields of food analysis, Surface area and more versatile surface performance
[8-10]
biomedical and environmental sanitation . Currently, carbon nanotubes
Processing before [2-5]. (CCNT), graphene (Graphene, G),
However, the polymer monolith polymer column Gold/silver nanoparticles, metal organic
is not polymerized in a controlled manner skeletons (metalorganic)
 and is under production
During the preparation process, particle
accumulation structures can be created, Frameworks, Mofs) and covalent organic skeletons
resulting in porosity (covalnet)
Low and limited surface area. In addition, Other countries such as the OFs, have been
the polymer is integral with the column successfully mixed into aggregations
Organic solvents are prone to bloating, which The material is rich in surface on the one
can affect their life and overall life hand in the column (see Figure 1)
The precision of the method. In recent years,
nanomaterials have been adulterated to Active submerges, action sites, and very large
polymers area of the surface can increase cohesion
The overall column, developed with an orderly Extraction performance or selectivity of
structural distribution, good absorption compound monolith columns, on the other hand,
efficiency, and can be modified
The novel adsorbent with superior selective Raise the column bed by improving the original
performance became a research hot spot [6, 7]. grain buildup and uneven holes
 Issue 3 Li Ziling, etc.: Construction of solid columns of nanomaterials adulterated polymers
and their application in the pretreatment field ·２３１
·
carbon atom with a diameter of 04 to 30 mm;
The MWNT is made up of multiple concentric tubes,
which can be up to 100 mm in diameter. The CNT
surface contains rich π electrons, which have
advantages such as hydrophobic properties, good
chemical stability, and good thermal stability,
and is up to 500 percent larger than the surface
area
ｍ２ ／ｇ［１６，１７］ 。
[18]
Fredcorex Cala et al. use methacrylate
reduced glyceride (GMA) as monomer and ethylene
glycol dimethyl methacrylate (EDMA) as cross-
Figure 1 Schematic illustration of a solid column of
nanomaterials doped to polymers linking agent, For the first time, the MWNT
Ｆｉｇ． １ Ｓｃｈｅｍａｔｉｃ ｄｉａｇｒａｍ ｏｆ ｎａｎｏｍａｔｅｒｉａｌｓ ｉｎｃｏｒｐｏｒａｔｅ GMAOcco EDMA solid-phase micro-extracting
ｄｍｏｎｏｌｉｔｈｉｃ ｃｏｌｕｍｎｓ ａｎｄ ｔｈｅｉｒ ａｐｐｌｉｃａｔｉｏｎ ｉｎ ｓａ
ｍ⁃ｐｌｅ ｐｒｅｐａｒａｔｉｏｎ monolith has developed a simple, efficient and
ＳＰＭＥ： ｓｏｌｉｄ ｐｈａｓｅ ｍｉｃｒｏｅｘｔｒａｃｔｉｏｎ； ＳＢＳＥ： ｓｔｉｒ ｂａｒ ｓ
low-cost pretreatment of antidepressants in
ｏｒｐｔｉｏｎｅｘｔｒａｃｔｉｏｎ．
biological samples through photocophmeric legal
Mechanical strength and stability of the . preparation at the tip of the pipette. The
[11-13]
MWNT's π function has enhanced the overall column
１．１ Carbon material
pair
Carbon's multiple isotopes show
structural diversity, such as zero-dimensional
Fullerene, one-dimensional carbon nanotubes
and two-dimensional graphene, and porous
carbon-material activated carbon. Carbon
materials have the advantages of good chemical
stability, larger than surface area and higher
absorption capacity, especially the fact that
the very large-surface π electronic conjugate
system produces π conjugates and hydrophobic
effects with some compounds and metal ions,
which make carbon materials an active home in
the area of adsorption and separation
Nationality [14,15].
１．１．１ Carbon nanotubes
CNT is a one-dimensional carbon nanometer
material curled by graphene sheet layers,
divided into single-wall carbon nanotubes
(singleresuwaledcarbonanonebe, SW NT) according to
the graphene layers And multi-wall carbon
nanotubes (MWNT). NWNT is a single-layer
 [23]
G et al. adulterated G to methylacrylate
Extraction efficiency of antidepressants. Wu et (BMA) as monomer and EDMA as a cross-linked
[19]
al. prepared monolith columns with MWNT and column, and hydrophobic, π conjugate and hydrogen-key
stirene (ST) as coamous monomer and EDMA as interactions of G enhance the abundance of
crosslinking agent for the treatment of bear fruit glycerides in the adulterated monolith column. The
acid in plant medicinal materials before solid glycocorticohormones in cosmetics were measured in
phase extraction. After mixing MWNT, the specific conjunction with the high-efficiency liquid
surface area of the polymer monolith increased from chromatography series mass spectrometry, with a
1275 M2/g to 4322 M2/g, and the absorptive capacity detection limit of 013 to 193n/UL and a recovery
[24]
of bear fruit acid increased significantly from 20 rate of 837% to 1038%. PEI et al. use 4 x vinyl
mg/g to 50 mg/g, but the weak polarity of MWNT can pyridine (4 x vinylpyril(CP) as functional monomer and
cause difficulties in dispersing the polymer EDMA as cross-linking agent, and use GMPPC as
solution during the overall column preparation polymer preparation (GMPPC) Treatment of benzoacetic
The effective solution is to treat MWNT acid herbicides in ambient water and rice is
[20]
carboxylate and then mix it up. Mackiliang et al. provided in front of the capillary column. When
with methylacrylate (MAA) as monomer and EDMA added, G increased the area of the surface from
as crosslinking agent, mixing carboxylated MWNT 415m2/g to 1362m2/g compared to blank columns, and
into polymeric (MAAlipcopo-EDMA) columns, As extracted the target through π, hydrophobic, ion
four types of hydroxyl benzoic acid in cosmetics exchange, and hydrogen keying, thus increasing the
and personal care products for pre-SPME concentration capacity of phenoxacetic acid by 22
adsorption, a low-cost extraction device was ～'s
established, enabling simultaneous and rapid The method is simple, sensitive and
extraction of six actual samples. Carboxylated environmentally friendly, providing a new
MWNT improves dispersion during preparation, idea for the detection of benzoacetic acid
and surface π conjugate and hydrogen keystroke herbicides in complex sample matrices.
Graphene oxide (Graphenoxide, GO) is graphene
increase the extractable efficiency of the four
hydroxyl benzoic acids in the column to 100%,
significantly higher than the blank column's
ratio of 535% to 918%. The method has a
detection limit of 063 to 0800 g/UL and a
recovery rate of 834% to 1029%. The column can
be reused at least 15 times, with a relative
standard deviation of ≤52%.
１．１．２ Graphene
G is a new carbon material that is tightly
stacked into a single layer, two-dimensional
honeycomb lattice structure, and is uniquely
equipped by the close accumulation method and
the characteristic of sp2 heterodization into
keying connections. Compared to carbon nanotubes, G
has a very large specific surface area with a
theoretical calculation of 2630 m2/g, Thus,
since the first acquisition in 2014, there has
[21,22] in the fields of biological
been a research boom
sensing, drug transmission, and separation science
.
 ·２３２ Colo
· r Spectra Vol. 39
An important derivative because it is in a
two-dimensional space made up of single-layer Phenolic acid, and the extraction efficiency increased
carbon atoms from 20% to 49% to 325%
The surface, which extends indefinitely,
contains large amounts of oxygen-containing 788%, which shows adulterated polymers that
groups such as hydroxyl and carboxyl aggregate purified phenolic acids
And carbohydration, epoxy, and carbohydration, Application
so they can be found in water and many other potential of
organisms compounds.
Solvents are dispersed well, hydrophilic and So, there are many reports on carbon-doped
biocompatible [25, 26]. polymer monolith research.
The main thing is to improve polymers is by
relying on the carbon material itself π to
The GOOMEA has been prepared conjugate effect
The column, which acts as an SPE adsorbent,
combines liquid chromatography with tandem Performance of the integral column. Carbon
mass spectrometry nanotubes and graphene are produced by
Determination of creatinine in urine. The Due to its weak polarity, it is gathering when
method has a detection limit of 10 g/UL, preparing adulterated polymer monolith columns
The recovery Dispersion in the solution is the first
rate was 78 5% to 962%, gather (GOOMEA) problem, choosing aggregation
［２８］
Prepare
The monolithic column can enrich the Monomers and tracers, solvents, are
myamid 32 times. Jigg, etc. gather relatively harsh. Make them on the surface
After derivation, the polymeric conditions
(GOOXMAA) monolith column combined with high- become loose, and the polymer monolith
efficiency liquid chromatography obtained is also obtained
The online SPME pretreatment of amino-methyl-
acid insecticides in environmental water More diversity.
The introduction of the agent and the GO has
improved the enrichment of the overall column １． Metals and metal
against the target object. ２ oxides
The detection limit Μg/L, with a recovery rate of １．２．
Gold/Silver
is 03-07 789%～ １ nanoparticles
The company has prepared the
１０３ ４％。 This subject whole of the company Gold/Silver nanoparticles are nanoparticles
group [29] (GAOMEDA) consisting of gold/silver atoms
The column acts as an online SPE purification
column in series with the high-efficiency Grain, which is usually 1 to 100 meters in diameter,
liquid chromatography veins has a high specific surface area
And good biological compatibility.
Together, the spectrum achieved 16 sulfonamides Gold/silver nanoparticles and sulfhydryl and
in milk and chicken ammonia
Rapid and automated assays. When the GO is One side
mixed, the specific surface of the monolithic Specific binding of Based on is
column isobs this feature available
/g, total method
２ ２ analysis time , ,
The
product is It was ok to build a polymer monolith with
65 m /g to 226m gold/silver nanoparticles mixed
The detection limit for milk and chicken was 23 Selective enrichment of analytes containing
min specific subgroups when applied [34].
Μg/kg with a recovery rate of 703% to 985%
Μg/kg and 06 respectively Mompó2 Roselló, ［３５］ Prepare the gather
And 790% to 1080%. etc. (Aumu GMAQOUCO)
 (EDMA) monolith column, combined with high-
efficiency liquid chromatography and
1.1.3. Activated Is the carbon photoluminescent detection, divided into two
carbon of a porous subdivided columns
Activated carbon ａｃｔｉｖｅ ｃａｒｂｏｎ , ＡＣ structure Analyze glutathione in urine and saliva (see Figure 2). Uses gold nanometers

( )
The amino and thiol pairs on the particle surface contain
sulfhydryl non-aromatic compounds
Material produced by thermal pyrolysis activation of the material in anaerobic or anaerobic environments

Material, with high mechanical strength, stable chemical properties, acid-base and heat
resistance, and strong affinity for material, The solid column of the
amplous column (AouregMAKICOMEDA) is rich in pore structure, with a large surface area ( the
sorption capacity of the 50-170 glutathion is 293mg/g and the
concentration factor is M2/g), and features on the surface containing active groups such as carboxylic,
hydroxy and carboxyl
Sex. In addition, the AC is widely
available, simple to prepare, inexpensive,
and renewable. As a result, good
application potential has been demonstrated in the field
of complex sample matrix pretreatment [30,
31].
Lilio et al. [32] prepare aggregates in
capillary tubes by direct adulteration
(ACKBOMA) and polystirene (ACKI)
(DIVNYL Benzenen, DVB)) as a solid column, adsorbed
as SPME
In combination with ultra-high-liquid
chromatography superviolet testing, the agent
analyzes five adjacencies in water
Benzodimethyl ester. The adulteration of AC
changes the polymer column surface
Polarity, enhances the hydrophilic nature of the
column, polymerization (AC BMAODI)
The extraction efficiency of phthalate ranged
from 15.9% of the blank column
531% increased to 542% to 797%, gathered Figu
(ACHOHOHOHOBOOHE DVB) re 2 The "Auluxue GMA" monolith SPE treated urine and
Increase to 762% to 993% and 30 reuse times. Ｋｕｏ Flow diagram
of glutathione in saliva[35]

And so on Prepared by microwave assisted legislation (ACMBMAI) ｆｒｏｍ ｕｒｉｎｅ ｕｓｉｎｇ ｐｏｌｙ（ Ａｕ⁃ＧＭＡ⁃ｃｏ⁃ＥＤＭＡ） ｉｎｃｏｒ⁃

［３３］ Ｆｉｇ．２ Ｆｌｏｗ⁃ｃｈａｒｔ ｏｆ ｓｏｌｉｄ ｐｈａｓｅ ｅｘｔｒａｃｔｉｏｎ ｏｆｇｌｕｔａｔｈｉｏｎｅ

Capillary monolith column for use in front of
phenolic acid in fruit wine and cranberry
juice ｐｏｒａｔｅｄ ｍｏｎｏｌｉｔｈｉｃ ｓｙｒｉｎｇｅ［
３５
］

Processing. Due to the hydrogen-bond and π-

knot conjugate created between AC and phenolic
acid ＧＭＡ： ｇｌｙｃｉｄｙｌ ｍｅｔｈａｃｒｙｌａｔｅ； ＥＤＭＡ： ｅｔｈｙｌｅｎｅ ｇｌｙｃｏｌ ｄｉｍｅ⁃
ｔｈａｃｒｙｌａｔｅ．
The polymer monolith with AC can be extracted simultaneously 9/ Species
 Issue 3 Li Ziling, etc.: Construction of solid columns of nanomaterials adulterated polymers
and their application in the pretreatment field ·２３３
·
ZnO nanoparticles into the MAA pentaum EDMA
58, the detection limit for the method is 153 monolith column for extracting four fluoroquinone-
ng/UL. After 15 times of polymer monolith type antibiotics in environmental water. ZnO is
reuse, the recovery rate for glutathion was able to merge with the target and create static
[36]
still greater than 90%. Jiang et al. electricity, successfully improving extraction
prepared a silver nanoparticles adulterated efficiency
polymer monomer using transparent acid 85 times, the method is simple and practical,
functionalized urea-dehydride for the single and is suitable for pre-treatment of
unsaturated fatty methyl ester in fries before fluorquinone in many actual samples. Kreenkofa
[40]
SPME. The surface area of the adulterated et al. Electrostatic used to adulterate the
monolith column has been increased from Fe3o4 to the surface of the polymer
650m2/g to 268m2/g. (GMAXOMDMA) for selective enrichment of
１．２．２ Metal Oxide phosphate peptides, and to increase the number
Metal oxide is a binary compound consisting of of phosphate peptides in alpha memotin
metal and oxygen elements, such as In2103, ZnO, solution from 5 to 19 that were not abundant.
[41]
Fe3104, and Al2103. Metal oxides are due to unique L et al. introduced gamma amplum Al2103
surface-active sites and special physicochemical into a poly(Nxopropylacrylamide dorex
properties GMAXBOXIDE) capillary column for extracting
The properties, which can be adulterated Sudanese dyes from red wine. After
into the overall column, on the one hand, adulteration of the gamma-double-A3, the
the hydroxyl on the surface can interact polymer column's enrichment capacity increased
with a specific functional group, providing significantly by 159~177 times.
more active sites to adsorb the target, On １．３ Metal organic skeleton
the other hand, the good biological
Mofs is a crystalline material made of
compatibility and chemical stability of
highly sequenced connections between metal ions
metal oxides make them the ideal material
or clusters and organic liges. The variety of
for adulterated polymer monolith columns.[37]
[38] metal ions and organic ligand and mating methods
Qi et al. assembled the In2103 with GMA and
MAA monomers, and prepared the In2103-plus of the MFs determine the diversity of the

GMAXIMOXA-plus EDMA monoll column as a SPME composition and structure of the MFs, while the
adsorbent for the pretreatment of 12 artificial MFs are larger than the surface area, have
pigments in foodstuffs. Due to the introduction of uniform aperture distribution, The surface
In2103, the mechanical properties and thermal properties are adjustable,
stability of the polymer column as a whole have
improved significantly, and the maximum temperature
of thermal decomposition (4105°C) is
significantly higher than that of blank columns
(2736°C). In addition, the large surface area and
surface rich hydroxyl of In2103 can produce
hydride-keying effects with 12 artificial pigments
such as Rodin B, quinoline, and Sunset Yellow,
significantly increasing the abundance of
[39]
adulterated columns. Luu et al. introduced the
 [50]
Wanng et al. prepared the COF-doped
It has demonstrated good practice in gas polymeric (GMAXED) capillary column in
storage, drug transmission and sorption
separation combination with the GMA surface epoxy
covalent key to analyze diphenylketonone in
Good application potential [42-44].
[45]
the blood in conjunction with the high-
Lyu et al. legally adulterated the
efficiency liquid chromatography exviolet test
MILQ53(Al) into the BMAXBOXCOMEX EDMA monolith
(see figure 3). There is an π and hydrogen
through in situ clustering, and combined with high-
keying effect between the Cofdoped monolith
efficiency liquid chromatography, to determine non-
and diphenylketone, which can effectively
steroidal anti-inflammatory drugs in water and
enrich diphenylketone 175 to 403 times. The
urine. After mixing the mix of the mix-up with the M3,
monolithic column was reused 50 times, with no
the area of the polymer monolith increased from 108
significant changes in extraction efficiency,
M2/g to 1076 M2/g, with no significant change in
and no significant collapse of the column bed.
extraction performance over 120 times of reuse. [51]
[46]
LI et al. synthesized copolymer (CFI stirene
Pung et al. use heat-induced polymerization to
dostirene restirene (GMA) monolith with high
prepare the MOF599 and NHYDROXIDE acrylamide as
concentration capacity for non-steroidal anti-
polymeric monomer polymer monolymers, combining
inflammatory drugs, and seven non-steroidal
high-efficiency liquid chromatography to establish
anti-inflammatory drugs in water pre-
methods for the analysis of bear fruit acid in
concentrated in the syringe. The
herbal medicines. After adulteration of the
absorbability of the monolithic column of
Mofl999, the area of the surface of the polymer
adulterated COF to target objects is
monolith increased from 873M2/g of the blank column to
significantly better than blank columns and
1829M2/g, and the sorption capacity of the bear
commercialized C18 sorbents, which can achieve
fruit acid increased from 1514 mg/g to 3729 mg/g.
[47]
an adsorption balance within 1 min, providing
Lin et al. prepared the MIL 101-plus BMA dosurex
a new idea for rapid extraction of non-
EDMA monolith column as a SPME adsorbent,
steroidal anti-inflammatory drugs or other
enabling an effective concentration of six
polar pollutants in environmental water.
penicillin in the river. With the addition of the
１．５ Inorganic nanomaterials
MINLQU101(Cr), penicillin is adsorbed through the Silicon dioxide (SiO2) is based on a silicon
interaction of Louistine and the π dovix yoke, oxygen tetrahedral
which can be detected up to 12 to 45 g/mol, and the
column can be reused more than 45 times.
１．４ Covalent organic skeleton
COFs are two-dimensional or three-
dimensional crystal porous materials connected
in covalent keys by light elements such as C,
H, O, N, and B. COFs are characterized by
large surface area, adjustable aperture,
variety and properties, low density, and
functional finish. In addition, covalent keys
dominated by B-O, C=N, and C-N make COFs
chemically and thermally stable. Currently,
COFs are widely used in the areas of
catalysis, optics, and pre-sample processing
[48, 49]
.
 ·２３４· Color Spectra Vol. 39
in
organic dyes and adsorption-separated proteins
environmental water [54, 55]
.
[56]
Krenkopva et al. legally adulterated the
HAP into polymeric (2-fold hydroxyl methyl
methacrylate endomethodorex (EDMA) through in-situ
concentration, for protein separation and selective
enrichment of phosphate peptides. Due to the
strong affinity between the HAP surface, the A2+
and the phosphate peptide, the adulteration of the
HAP enhances the selectivity of the whole column of
phosphate peptides and is able to enrich both
[57]
phosphate peptides effectively. Wang et al.
uses urea-dehyde as a monomer and polyglycol 600
Figure 3 preparation schematic of the COFQUEMAXED
[50]
monolith Fieg.3 sytheschemefpicture(COFQUEMAIDMA) To prepare HAP-doped polymer monolith for
５０
ｍｏｎｏｌｉｔｈ［ ］
ＣＯＦ： ｃｏｖａｌｅｎｔ ｏｒｇａｎｉｃ ｆｒａｍｅｗｏｒｋｓ． porosity, using a one-step polymeric reaction,
and combining high-efficiency liquid
The formed three-dimensional mesh structure has
chromatography dodiode array detection, a new
advantages such as a large surface area, high
method for analyzing adenosine triphosphate
mechanical strength, good biological
and its phosphate metabolites in grass fish
compatibility, and stable physico-chemical
properties; The surface contains rich hydroxyl was established, utilizing the hydrophilic and
silicates, which can be modified by chemical ion exchange of HAP and urea. That's right
branches and increased interaction with the
target by modified additional subgroups. Based
in the
on this, SIO2 has good application potential
areas of separation, pre-sample processing, catalytic and biomedical [52]
.
[53]
Xu et al. isolate and adsorb
proteins through the co-poly system of
polymeric columns adulterated with Sio2
nanoparticles, using acrylamide and N,
Nolumex, and double acrylamide as monomers.
The introduction of SiO2 nanoparticles has
led to significant improvements in the
porosity, permeability and mechanical
strength of the polymer column.
Hyderoxyapatite (HAP) is a calcium phosphate
compound of a class 1 molecular formula of
Ca10(Por4)6(Oh)2 and is constructed of a hex
column. As the main inorganic ingredient of
human bone tissue, HAP has good biological
compatibility and bioactivity, taking advantage
of the properties of its surface, the CA2 + and OH-can
be replaced by other metal ions. It is widely
used in the removal of inorganic metal ions,
 布不均和纳米材料流失等问题，同时，纳米材料也会
Adenosine triphosphate and its phosphate 包埋在柱床中，从而限制其有效使用，掺杂过量会导
metabolites achieve good purification and 致聚集甚至沉淀，无法达到良好的萃取效果。 另
enrichment, and reduce the response value of
外，直接掺杂法对聚合溶液的种类和极性有一定条件
impurity peaks by six times. The detection
limit is reached 要求，对于粒径大、密度大或表面极性弱等在聚合
01 to 04 μg/g, with a recovery rate of 783% to 925%.

２ How to construct monolith columns

of nanomaterials adulterated polymers
２．１ Direct adulteration
At first, nanomaterials were mainly introduced
［２９］
into polymer columns by simple adulteration, which 图４ 聚（ＧＯ⁃ＥＤＭＡ）整体柱的制备示意图
Ｆｉｇ． ４ Ｄｉａｇｒａｍ ｏｆ ｔｈｅ ｆａｂｒｉｃａｔｉｏｎ ｐｒｏｃｅｓｓ ｏｆ ｔｈｅ
means that nanomaterials, monomers, crosslinking ２９
ｐｏｌｙ（ ＧＯ⁃ＥＤＭＡ） ｍｏｎｏｌｉｔｈｉｃ ｃｏｌｕｍｎ［ ］

agents, and ignants are uniformly mixed in tractive

agents. Injected into the mold to build polymer
monolith columns by heat or light-induced polymers.
[29]
This topic group prepared the polymer (GAOMEDMA)
column directly through heat-induced free-based
polymerization in stainless steel columns as an online
SPE adsorbent, and developed simple and fast methods
for analyzing 16 sulfonamide drugs in chicken and milk
(see Figure 4). The overall column structure of the GO
adulterated is more uniform than the blank column
(65m2/g), with a larger than-surface area (226m2/g).
At the same time, the column's stability has been
improved, and after 450 reuse, the extraction
efficiency of sulfonamide drugs has not changed
significantly, with a relative standard deviation of
[33]
≤118%. Kuo et al. mix AC with BMA, EDMA and
trachete, which after ultrasound treatment is filled
in capillary heat and is induced for use in solid
phase microextraction of phenolic acid in foods. The
introduction of AC has significantly increased the
area of the overall column from 7m2/g to 352m2/g, and
the column has been reused at least nine times. Zhaung
[58]
et al. prepared polymerized (gamma-alpha-2-3-x
MAXOXOXOXOXOXMA) monoll columns with light-
induced in-situ aggregations for solid phase micro-
extraction of 2-core amino-4-pentachlorophenol in
clazole tablets. 掺杂 γ⁃Ａｌ ２ Ｏ ３ 的整体柱的比表面积增
加，对４⁃氯苯酚的富集倍数由７ ３ 提升至１７ ０。

以纳米材料直接掺杂方式构筑聚合物整体柱，
制备简单直接，无须复杂的化学修饰过程，但纳米材
料与单体之间没有化学键合，通常易导致纳米材料分
 第３ 期 李子凌，等：纳米材料掺杂聚合物整体柱的构筑及在前处理领域的应用 ·２３５·

溶液中分散困难的纳米材料存在局限性，难以通过 整体柱，再经一定方法将纳米材料修饰到整体柱表
这一方法实现掺杂。 面。 该方法主要依赖聚合物整体柱单体本身的官能
２．２ 共聚法 团进行反应，由于ＧＭＡ 表面的活性环氧基团可以
共聚法是将纳米材料与单体通过化学键合或在 与巯基、氨基等基团反应，而成为最常用的聚合单
纳米材料上修饰活性功能基团，再与交联剂聚合的 体。 Ｍｏｍｐ ó⁃Ｒｏｓｅｌｌ ó 等［３５］ 使用二苯甲酮和ＥＤＭＡ
方法。 Ｌｕｏ 等［５９］ 在ＭＩＬ⁃５３（ Ａｌ） 表面修饰氨基后， 对聚丙烯注射器内表面进行改性，实现与整体柱柱
与ＭＡＡ 表面的羧基结合形成酰胺键，热引发原位 床共价连接，通过光引发自由基聚合法制备聚
聚合法制备ＭＩＬ⁃５３（ Ａｌ） 掺杂的聚（ Ｓｔ⁃ＤＶＢ⁃ＭＡＡ） （ＧＭＡ⁃ｃｏ⁃ＥＤＭＡ）整体柱，表面分别修饰氨基、半胱
毛细管整体柱，用于在线固相微萃取尿液中的雌激 胺和胱胺后，将金纳米粒子与修饰的官能团结合掺
素。 掺杂后的整体柱对雌激素的富集倍数高达１８０ 杂，制备聚（ Ａｕ⁃ＧＭＡ⁃ｃｏ⁃ＥＤＭＡ） 整体柱对尿液和唾
［６０］
～ ３０４，且可重复使用 １００ 次。 Ｇｉｅｓｂｅｒｓ 等 在 液中谷胱甘肽进行前处理（见图５）。 整体柱重复使
ＭＩＬ⁃１０１ 表面修饰氨基与 ＧＭＡ 表面环氧基共价键 用１５ 次后，对谷胱甘肽的回收率仍大于９０％。 张爱
结合，通过原位聚合法制备聚（ ＭＩＬ⁃１０１⁃ＧＭＡ⁃ｃｏ⁃ 珠等［６２］ 在毛细管中制备聚（ ＧＭＡ⁃ｃｏ⁃ＥＤＭＡ） 整体
ＥＤＭＡ）整体柱，对尿液中３ 种非甾体类抗炎药进行 柱，表面修饰巯基后，利用金纳米粒子与巯基结合将
前处理。 掺杂ＭＩＬ⁃１０１ 后的整体柱重复使用５０ 次 其固定在聚合物整体柱表面，合成金纳米粒子掺杂
后，对非甾体类抗炎药的回收率仍大于７５％。 Ｌｉｕ 的聚合物整体柱作为ＳＰＭＥ 吸附剂，萃取血浆中谷
［６１］
等 将１，３，５⁃三羟基均苯三醛与甲基丙烯酸酐 胱甘肽。 由于金纳米粒子的引入，整体柱可对血浆
（ｍｅｔｈａｃｒｙｌｉｃ ａｎｈｙｄｒｉｄｅ， ＭＡ）通过酯化反应结合， 中谷胱甘肽有效富集３０ 倍。 Ｊｉａｎｇ 等［３６］ 首先制备
构建含有ＭＡ 的ＣＯＦ 材料为单体、ＥＤＭＡ 为交联剂 了透明质酸钠高性能化脲醛整体柱，使用脲甲醛进
的聚合物整体柱，ＣＯＦ 掺杂的整体柱结构均匀，通 行修饰，银纳米粒子与脲甲醛相互作用，开发了银纳
透性好，在分离多环芳烃、酚类和胺类化合物等有机 米粒子掺杂的聚合物整体柱，分析炸薯条中的单不
小分子方面分离度和精密度良好。 饱和脂肪酸甲酯。 掺杂后整体柱的比表面积由
使用共聚法制备的纳米材料掺杂整体柱中纳米 ６ ５０ ｍ２ ／ｇ 提升至 ２６ ７８ ｍ２ ／ｇ，重复使用 １００ 次后，
材料可以和聚合物柱床通过共价键连接，结构更稳 目标物的峰面积无明显改变。
定，但是在合成中首先需要对单体进行功能化，同时 通过后修饰法制备聚合物整体柱，将纳米材料
对聚合条件需要优化，相比直接掺杂法略显复杂。 化学键合到基体表面，获得的整体柱性质稳定，表面
２．３ 后修饰聚合法 均匀，纳米材料的覆盖率更佳，但是需要控制聚合物

后修饰方法是先合成不添加纳米材料的聚合物 整体柱载体的孔结构和纳米材料的覆盖率。

［３５］
图５ 聚（ ＧＭＡ⁃ｃｏ⁃ＥＤＭＡ） 整体柱表面分别修饰（ ａ） 氨基、（ ｂ） 半胱胺和（ ｃ） 胱胺后与金纳米粒子结合的示意图
Ｆｉｇ． ５ Ｓｃｈｅｍｅ ｏｆ ｆｕｎｃｔｉｏｎａｌｉｚａｔｉｏｎ ｏｆ ｐｏｌｙ（ ＧＭＡ⁃ｃｏ⁃ＥＤＭＡ） ｉｎ ｓｙｒｉｎｇｅ ｗｉｔｈ （ ａ） ａｍｍｏｎｉａ， （ ｂ） ｃｙｓｔｅａｍｉ
３５
ｎｅ ａｎｄ（ｃ） ｃｙｓｔａｍｉｎｅ， ａｎｄ ｓｕｂｓｅｑｕｅｎｔｌｙ ｉｍｍｏｂｉｌｉｚａｔｉｏｎ ｗｉｔｈ ｇｏｌｄ ｎａｎｏｐａｒｔｉｃｌｅｓ［ ］
·２３６· 色 谱 第３９卷
２ ２
面积由４７ ０ｍ ／ｇ 提升至 １５３ ８ ｍ ／ｇ，蜕皮
类固醇与吸附剂的
３ 纳米材料掺杂聚合物整体柱在前处理领
域的应用

样品前处理是指从复杂样品基质中净化和富
集目标物，使原始样品中的待测组分转化为适用
于仪器分析测定的形式，是分析过程中重要且必
要的环节。 样品前处理过程直接影响分析方法的
精密度、选择性、可靠性以及分析成本，成为制
约检测技术的瓶颈［６３－６５］ 。
作为样品前处理技术的核心，吸附剂决定了前
处理的选择性和效率。 纳米材料掺杂聚合物整体柱
同时具备纳米材料比表面积大和吸附性能好的优良性
能以及聚合物整体柱结构连续多孔、通透性好、柱压
低和传质快的优点，通过ＳＰＥ、ＳＰＭＥ、搅拌棒吸附
萃取（ＳＢＳＥ）和在线ＳＰＥ 等模式成功用于生物医
药、环境卫生和食品安全领域样品前处理。
３．１ 固相萃取
ＳＰＥ 技术是利用样品在两相（ 吸附剂和溶剂）
之间分配系数的差异有效地将目标化合物与复杂基
体分离，实现目标物净化与富集的一种前处理技
术［６６－６８］ 。 ＳＰＥ 具有有机溶剂消耗少和萃取
效率高等优势，近年来，基于纳米材料掺杂的聚
合物整体柱作为固相萃取吸附剂在样品前处理领
域已成为研究热点。
Ａｌ⁃Ｒｉｆａｉ 等［６９］ 以甲基丙烯酸苄酯 （ ｂｅｎｚｙｌｍｅｔ
ｈａｃｒｙｌａｔｅ， ＢｚＭＡ） 为单体、ＥＤＭＡ 为交联剂，制备聚
（ ＣＮＴ⁃ＢｚＭＡ⁃ｃｏ⁃ＥＤＭＡ ） 整体柱，作为ＳＰＥ 吸附
剂，结合高效液相色谱，测定水中多环芳烃。 ＣＮＴ
的掺杂使整体柱对多环芳烃的萃取效率提升了４８ ６％
～７８ ４％，富集倍数高达 １００ 倍，方法检出限为０
０２～０ ２２ μ ｇ／Ｌ。 本课题组［７０］ 将ＧＯ 与ＥＤＭＡ
直接聚合，在注射器柱管中热引发制备了聚（ ＧＯ⁃ＥＤＭ
Ａ）整体柱作为 ＳＰＥ 吸附剂，建立了尿液中 ６种羟基多
环芳烃的前处理方法（见图６）。 ＧＯ 的引入增强柱床与
羟基多环芳烃的 π⁃π 共轭作用，将萃取效率由空白柱的
７０ ７％ ～８６ ３％ 提升至９４ ２％ ～１０１％。
该方法简单、高效，为尿液中羟基多环芳烃的分析提供了
新方法，为复杂样品基质中羟基多环芳烃的前处理提供了
新思路。 Ｗａｎｇ 等 ［７１］ 在注射器中构筑亚氨基多孔金
属有机笼掺杂聚ＥＤＭＡ 整体柱，结合高效液相色谱⁃串联
质谱法，分析藜麦样品中的蜕皮类固醇。 掺杂整体柱比表
 图６ （ ａ） 聚（ ＧＯ⁃ＥＤＭＡ） 整体柱的构筑和（ ｂ） 聚（ ＧＯ⁃ＥＤ
［７０］
ＭＡ）整体柱ＳＰＥ 前处理尿液中羟基多环芳烃流程图
Ｆｉｇ． ６（ａ） Ｆａｂｒｉｃａｔｉｏｎ ｐｒｏｃｅｓｓ ｏｆ ｐｏｌｙ（ＧＯ⁃ＥＤＭＡ） ｉｎｃｏｒ
⁃ｐｏｒａｔｅｄ ｍｏｎｏｌｉｔｈｉｃ ｓｙｒｉｎｇｅ ａｎｄ （ ｂ） ｆｌｏｗ⁃ｃｈａｒｔ ｏｆ
ＳＰＥ ｏｆ ｈｙｄｒｏｘｙｌａｔｅｄ ｐｏｌｙｃｙｃｌｉｃ ａｒｏｍａｔｉｃ ｈｙｄｒｏｃａｒ
⁃ｂｏｎｓ ｆｒｏｍ ｕｒｉｎｅ ｕｓｉｎｇ ｐｏｌｙ（ ＧＯ⁃ＥＤＭＡ） ｉｎｃｏｒｐｏ⁃
７０
ｒａｔｅｄ ｍｏｎｏｌｉｔｈｉｃ ｓｙｒｉｎｇｅ［ ］

作用主要为疏水、π⁃π、范德华力和氢键作用。
３．２ 固相微萃取
ＳＰＭＥ 是以某种纤维或者材料作为载体，在其
表面涂覆不同性质的吸附材料薄膜，通过直接或顶空
微萃取的方式，实现对样品的吸附、进样和脱附，具
有操作简单、萃取速度快、有机溶剂消耗少且环境友
好等优点，可实现对痕量目标物集取样、萃取、浓缩
和进样于一体的绿色前处理方法 ［７２，７３］ 。 ＳＰＭＥ
涂层决定了萃取的选择性、容量和速度，从而影响整
个分析方法的灵敏度和使用范围。 基于纳米材料掺
杂的整体柱具有高吸附容量和高通透性能等优点，近
年来已成为广泛应用的ＳＰＭＥ 涂层材料。
Ｆｒｅｓｃｏ⁃Ｃａｌａ 等 ［７４］ 以 ＧＭＡ 为单体、 ＥＤＭＡ
为交联剂，光引发制备的碳纳米角掺杂的聚合物整体柱作
为ＳＰＭＥ 吸附剂预处理尿液中４ 种非甾体抗炎药。 该
柱光引发１０ ｍｉｎ 即可完成制备， 简单快速。 相比空
白柱的比表面积（＜１０ ｍ ２ ／ｇ），掺杂碳纳米角的整
体柱比表面积显著增加至７００ ｍ ２ ／ｇ，同时增强了整
体柱的机械强度和化学稳定性，并通过 π⁃π 和氢键作用吸
附目标物， 检出限为 ０ １ ～ １０
 第３ 期 李子凌，等：纳米材料掺杂聚合物整体柱的构筑及在前处理领域的应用 ·２３７
·

μ ｇ／Ｌ。 Ｌｕｏ 等 ［５９］ 通过热引发成功制备聚（ ＮＨ ２ ⁃ 类除草剂作用，使得聚合物整体柱对目标物的萃取

ＭＩＬ⁃５３⁃Ｓｔ⁃ＤＶＢ⁃ＭＡＡ） 整体柱作为 ＳＰＭＥ 涂层用于 效率提升３ ７～４ ５ 倍。
尿液中雌激素的前处理，掺杂ＭＩＬ⁃５３ 的整体柱与雌激素 ３．４ 在线固相萃取
之间存在疏水、π⁃π 和氢键作用，可有效富集目标物达到
在线固相萃取是将固相萃取净化柱作为第一维色
１８０～３０４ 倍，检出限为２ ０～４０ ｎｇ／Ｌ，方法
谱柱完成上样、淋洗、洗脱及条件化等步骤后，将富
无须进一步的净化程序， 简便且灵敏。 Ｌｉｒｉｏ等［７５］ 采
集净化后的目标物通过切换阀转移至第二维色谱柱的
用微波辅助法将ＢＭＡ、ＥＤＭＡ 以及不同比例的铝基金属 分析柱上，完成目标物的分离与分析。 在线固相萃
有机骨架ＭＩＬ⁃５３ 聚合，制备聚（ ＭＩＬ⁃５３⁃ＢＭＡ⁃ｃｏ⁃Ｅ 取操作简单，避免离线操作过程中样品损失和遭受污
ＤＭＡ）整体柱，作为 ＳＰＭＥ 吸附剂前处理河水和牛奶中 染，减小操作误差，分析速度快 ［８０，８１］ 。 在线
青霉素。 ＭＩＬ⁃５３ 与青霉素通过 π⁃π 和氢键作用，使得 固相萃取净化柱是整个在线净化系统的核心。 聚合
方法检出限低（０ ０６０～０ ２６ μ ｇ／Ｌ），且线性范 物整体柱制备简单，可以在毛细管柱、不锈钢柱和移
围宽（３０～３ ０００ μ ｇ／Ｌ） 。 液枪枪尖等多种模具中构筑，便于与仪器联用。 纳
３．３ 搅拌棒吸附萃取 米掺杂的整体柱同时兼具聚合物和纳米材料的双重作
ＳＢＳＥ 是在 ＳＰＭＥ 基础上建立的一种绿色、 用，将其与在线固相萃取技术结合可实现固相萃取净
环保的样品前处理技术，主要采用浸没方式将涂层与 化和分离分析的自动化。
样品直接接触从而吸附目标分析物，具有操作简便、 杨成雄等［８２］ 将ＭＩＬ⁃１０１ 掺杂的聚合物整体柱
溶剂用量少、富集倍数高和环境友好等优点 ［７６，７ 用于在线ＳＰＥ 环境水中４ 种酚类化合物。 ＭＩＬ⁃１０１加
７］
。但搅拌棒在搅拌过程中与容器的接触会造成磨 入后，在 π⁃π 共轭和氢键相互作用下，提高了整体柱的富
损，降低使用寿命。 纳米材料掺杂的整体柱可以提 集能力，富集因子为７１～１２７。 Ｃｕｉ 等［８３］以１⁃辛
高柱床的机械强度和稳定性，从而有效萃取目标物， 烯（１⁃ｏｃｔｅｎｅ， Ｃ８） 为单体，三甘醇二甲基丙烯酸酯
近年来作为ＳＢＳＥ 涂层备受青睐。 （ＴＥＧＤＡ）为交联剂，通过原位自由基共聚法制备ＧＯ 掺
［７８］
Ｙｏｕ 等 将 ＺＩＦ⁃８、单体和致孔剂均匀混合， 杂的聚合物整体柱，用于在线固相萃取食用油中 β⁃谷甾
通过一锅法制备聚（ ＺＩＦ⁃８⁃甲基丙烯酸甲酯⁃ｃｏ⁃ＥＤＭＡ） 醇。 ＧＯ 的掺杂使整体柱对目标物的吸附容量（８２ ５
整体柱用于 ＳＢＳＥ 前处理水果中 ５ 种植物激素。 ＺＩＦ⁃ ｍｇ／ｇ） 明显高于空白柱（３４ ６ｍｇ／ｇ） 。 同时该
８ 的引入增大了整体柱的比表面积，与植物激素之间的静 课题组［８４］ 采用纳米金刚石掺杂的聚合物整体柱， 在线

电、疏水、氢键和 π⁃π 共轭作用，使得整体柱的萃取效 固相萃取食物油中的 β⁃谷甾醇。 加入纳米金刚石后，聚

率（４８％ ～５７％） 明显高于空白柱（４％ ～３ 合物整体柱的比表面积由４ ９６ ｍ２ ／ｇ 提升至２０ ９

２％） 和商品化ＳＢＳＥ 吸附剂（２％ ～３７％）。Ｙａｎ ７ ｍ ２ ／ｇ，耐受的最高温度（３００ ℃）高于空白柱

ｇ 等［７９］ 制备 ＵｉＯ⁃６６ 掺杂的聚合物整体柱作为ＳＢＳ （２４５ ℃）。

Ｅ 涂层，用于土壤和湖水中 ５ 种磺酰脲类除草剂的分 综上，纳米材料掺杂聚合物整体柱的制备和应

析。 ＵｉＯ⁃６６ 通过氢键和 π⁃π 共轭与磺酰脲 用见表１。
表１ 纳米材料掺杂的聚合物整体柱的制备和应用
Ｔａｂｌｅ １ Ｐｒｅｐａｒａｔｉｏｎ ａｎｄ ａｐｐｌｉｃａｔｉｏｎ ｏｆ ｎａｎｏｍａｔｅｒｉａｌｓ ｉｎｃｏｒｐｏｒａｔｅｄ ｐｏｌｙｍｅｒｉｃ ｍｏｎｏｌｉｔｈｓ

Ｃｏｍｏｎｏｍｅｒ Ｐｒｅｔｒｅａｔｍｅｎｔ
Ｎａｎｏｍａｔｅｒｉａｌ Ｉｎｉｔｉａｔｉｏｎ Ｓａｍｐｌｅ Ａｎａｌｙｔｅ Ｒｅｆ．
ｓｙｓｔｅｍ ｍｏｄｅ

ＧＭＡ／ＥＤＭＡ ＭＷＣＮＴ ＵＶ／３０ ｍｉｎ ＳＰＭＥ ｕｒｉｎｅ ａｎｔｉｄｅｐｒｅｓｓａｎｔｓ １８

Ｓｔ／ＥＤＭＡ ＭＷＣＮＴ ３０ ℃ ／ ３ ｈ ｏｎ⁃ｌｉｎｅ ＳＰＥ ｍｅｄｉｃｉｎａｌ ｐｌａｎｔｓ ｕｒｓｏｌｉｃ ａｃｉｄ １９

ＭＡＡ／ＥＤＭＡ ＭＷＣＮＴ ＡＩＢＮ／６０ ℃／２４ ｈ ＳＰＭＥ ｃｏｓｍｅｔｉｃ ａｎｄ ｐｅｒｓｏｎａｌ ｐａｒａｂｅｎｓ ２０

ｃａｒｅ ｐｒｏｄｕｃｔｓ
ＢｚＭＡ／ＥＤＭＡ ＣＮＴ ＡＩＢＮ／７０ ℃／２０ ｈ ＳＰＥ ｗａｔｅｒ ｐｏｌｙｃｙｃｌｉｃ ａｒｏｍａｔｉｃ ｈｙｄｒｏｃａｒ⁃ ６９

ｂｏｎｓ
ＧＭＡ／ＥＤＭＡ ｃａｒｂｏｎ ｎａｎｏｈｏｒｎｓ ＵＶ ＳＰＥ ｕｒｉｎｅ ｎｏｎ⁃ｓｔｅｒｏｉｄａｌ ａｎｔｉ⁃ｉｎｆｌａｍｍａｔｏｒｙ ７４
 ｄｒｕｇｓ
ＢＭＡ／ＥＤＭＡ Ｇ ＡＩＢＮ／６０ ℃／４８ ｈ ＳＰＭＥ ｃｏｓｍｅｔｉｃ ｇｌｕｃｏｃｏｒｔｉｃｏｉｄｓ ２３
 ·２３８
· 色 谱 第３９卷
表１ （续）
Ｔａｂｌｅ １ （Ｃｏｎｔｉｎｕｅｄ）

Ｃｏｍｏｎｏｍｅｒ Ｐｒｅｔｒｅａｔｍｅｎｔ
Ｎａｎｏｍａｔｅｒｉａｌ Ｉｎｉｔｉａｔｉｏｎ Ｓａｍｐｌｅ Ａｎａｌｙｔｅ Ｒｅｆ．
ｓｙｓｔｅｍ ｍｏｄｅ

ＶＰ／ＥＤＭＡ Ｇ ＡＩＢＮ／７０ ℃／１２ ｈ ＳＰＭＥ ｗａｔｅｒ ａｎｄ ｒｉｃｅ ｐｈｅｎｏｘｙａｃｅｔｉｃ ａｃｉｄ ｈｅｒｂｉｃｉｄｅｓ ２４

ＧＭＡ／ＥＤＭＡ ＧＯ ＡＩＢＮ／６０ ℃ ＳＰＭＥ ｕｒｉｎｅ ｓａｒｃｏｓｉｎｅ ２７

ＭＡＡ／ＥＤＭＡ ＧＯ ＡＩＢＮ／６５ ℃／２４ ｈ ＳＰＭＥ ｅｎｖｉｒｏｎｍｅｎｔａｌ ｗａｔｅｒ ｃａｒｂａｍａｔｅ ｉｎｓｅｃｔｉｃｉｄｅｓ ２８

ＥＤＭＡ ＧＯ ＡＩＢＮ／６０ ℃／３０ ｈ ｏｎ⁃ｌｉｎｅ ＳＰＥ ｍｉｌｋ ａｎｄ ｃｈｉｃｋｅｎ ｍｕｓｃｌｅ ｓｕｌｆｏｎａｍｉｄｅｓ ２９

ＥＤＭＡ ＧＯ ＡＩＢＮ／６５ ℃／２５ ｈ ＳＰＥ ｕｒｉｎｅ ｈｙｄｒｏｘｙｌ ｐｏｌｙｃｙｃｌｉｃ ａｒｏｍａｔｉｃ ７０

３０ ℃ ／ ２．５ ｈｙｄｒｏｃａｒｂｏｎｓ
Ｃ８ ／ＴＥＧＤＡ ＧＯ ｈ ｏｎ⁃ｌｉｎｅ ＳＰＥ ｅｄｉｂｌｅ ｏｉｌ β⁃ｓｉｔｏｓｔｅｒｏｌ ８３

ＢＭＡ／ＥＤＭＡ ＡＣ ＡＩＢＮ／ｍｉｃｒｏｗａｖｅ／ ＳＰＭＥ ｄｒｉｎｋｉｎｇ ｗａｔｅｒ ｐｈｔｈａｌａｔｅ ｅｓｔｅｒｓ ３２

９００Ｗ／ ５ｍｉｎ
ＢＭＡ／ＥＤＭＡ ＡＣ ＡＩＢＮ／ｍｉｃｒｏｗａｖｅ／ ＳＰＭＥ ｆｒｕｉｔ ｗｉｎｅ ａｎｄ ｃｒａｎｂｅｒｒｙ ｐｈｅｎｏｌｉｃ ａｃｉｄ ３３

ｍｉｎ
９００Ｗ／ ５ ｊｕｉｃｅ
ＧＭＡ⁃ＥＤＭＡ ＡｕＮＰｓ ＵＶ／１０ ｍｉｎ ＳＰＥ ｓａｌｉｖａ ａｎｄ ｕｒｉｎｅ ｇｌｕｔａｔｈｉｏｎｅ ３５

ＧＭＡ⁃ＥＤＭＡ ＡｕＮＰｓ ＡＩＢＮ／６０ ℃／２４ ｈ ＳＰＭＥ ｂｌｏｏｄ ｐｌａｓｍａ ｇｌｕｔａｔｈｉｏｎｅ ６２

ＵＦ ＡｇＮＰｓ ７０ ℃／１０ ｍｉｎ ＳＰＭＥ ｆｒｅｎｃｈ ｆｒｉｅｓ ｍｏｎｏｕｎｓａｔｕｒａｔｅｄ ｆａｔｔｙ ａｃｉｄ ３６

ｍｅｔｈｙｌ ｅｓｔｅｒｓ
ＭＡＡ⁃ＧＭＡ／ Ｉｎ２ Ｏ３ ＡＩＢＮ／６０ ℃／２０ ｈ ＳＰＭＥ ｆｏｏｄ ｓｙｎｔｈｅｔｉｃ ｃｏｌｏｒａｎｔｓ ３８

ＥＤＭＡ
ＭＡＡ／ＥＤＭＡ ＺｎＯ ＡＩＢＮ／６０ ℃／２４ ｈ ＳＰＭＥ ｅｎｖｉｒｏｎｍｅｎｔａｌ ｗａｔｅｒ ｆｌｕｏｒｏｑｕｉｎｏｌｏｎｅ ａｎｔｉｂｉｏｔｉｃｓ ３９

ＮＩＰＡＡｍ／ γ⁃Ａｌ２ Ｏ３ ６５ ℃／１６ ｈ ＰＭＭＥ ｒｅｄ ｗｉｎｅ ｓｕｄａｎ ４１

ＧＭＡ／ＥＤＭＡ
ＭＡＡ／ＥＤＭＡ γ⁃Ａｌ３ Ｏ４ ＡＩＢＮ／ＵＶ／３ ｈ ＳＰＭＥ ｃｈｌｏｒｚｏｘａｚｏｎｅ ｔａｂｌｅｔｓ ２⁃ａｍｉｎｏ⁃４⁃ｃｈｌｏｒｏｐｈｅｎｏｌ ５８

ＢＭＡ／ＥＤＭＡ ＭＩＬ⁃５３ （ Ａｌ） ＡＩＢＮ／６０ ℃／１２ ｈ ＳＰＭＥ ｗａｔｅｒ ａｎｄ ｕｒｉｎｅ ｎｏｎ⁃ｓｔｅｒｏｉｄａｌ ａｎｔｉ⁃ｉｎｆｌａｍｍａｔｏｒｙ ４５

３０ ℃ ／ ３．５ ｄｒｕｇｓ
ＮＭＡ／ＥＤＭＡ ＭＯＦ⁃１９９ （ Ａｌ） ｈ ｏｎ⁃ｌｉｎｅ ＳＰＥ Ｃｈｉｎｅｓｅ ｈｅｒｂａｌ ｍｅｄｉｃｉｎｅ ｕｒｓｏｌｉｃ ａｃｉｄ ４６

ＢＭＡ／ＥＤＭＡ ＭＩＬ⁃１０１ （ Ｃｒ） ＡＩＢＮ／ｍｉｃｒｏｗａｖｅ／ ＳＰＭＥ ｒｉｖｅｒ ｗａｔｅｒ ｐｅｎｉｃｉｌｌｉｎ ４７

９００Ｗ／ ５ ｍｉｎ
Ｓｔ／ＤＶＢ／ＭＡＡ ＭＩＬ⁃５３ （ Ａｌ） ＡＩＢＮ／７０ ℃／２４ ｈ ｏｎ⁃ｌｉｎｅ ＳＰＭＥ ｕｒｉｎｅ ｅｓｔｒｏｇｅｎｓ ５９

ＧＭＡ／ＥＤＭＡ ＭＩＬ⁃１０１ （ Ｃｒ） ＵＶ ＳＰＭＥ ｕｒｉｎｅ ｎｏｎｓｔｅｒｏｉｄａｌ ａｎｔｉ⁃ｉｎｆｌａｍｍａｔｏｒｙ ６０

ｄｒｕｇｓ
ＢＭＡ⁃ＥＤＭＡ ＭＩＬ⁃５３ （ Ａｌ） ＡＩＢＮ／ｍｉｃｒｏｗａｖｅ／ ＳＰＭＥ ｒｉｖｅｒ ｗａｔｅｒ ａｎｄ ｍｉｌｋ ｐｅｎｉｃｉｌｌｉｎｓ ７５

９００Ｗ／ ５ ｍｉｎ
ＭＭＡ／ＥＤＭＡ ＺＩＦ⁃８ ＡＩＢＮ／６０ ℃／２４ ｈ ＳＢＳＥ ｆｒｕｉｔ ｐｈｙｔｏｈｏｒｍｏｎｅｓ ７８

ＶＰ／ＥＤＭＡ ＵｉＯ⁃６６ （ Ｚｒ） ＡＩＢＮ／５５－６０ ℃ ／ ＳＢＳＥ ｗａｔｅｒ ａｎｄ ｓｏｉｌ ｓｕｌｆｏｎｙｌｕｒｅａ ｈｅｒｂｉｃｉｄｅｓ ７９

３ ｄａｙｓ
ＧＭＡ／ＥＤＭＡ ＭＩＬ⁃１０１ ＡＩＢＮ／７０ ℃／２４ ｈ ｏｎ⁃ｌｉｎｅ ＳＰＥ ｅｎｖｉｒｏｎｍｅｎｔａｌ ｗａｔｅｒ ｐｈｅｎｏｌｓ ８２

ＧＭＡ／ＥＤＭＡ ＣＯＦ ＡＩＢＮ／６０ ℃／２０ ｈ ＳＰＭＥ ｕｒｉｎｅ ａｎｄ ｓｅｒｕｍ ｂｅｎｚｏｐｈｅｎｏｎｅｓ ５０

Ｓｔ⁃ｄｉｖｉｎｙｌ／ ＣＯＦ １２０ ℃ ／ ７２ ｈ ＳＰＥ ｅｎｖｉｒｏｎｍｅｎｔａｌ ｗａｔｅｒ ｎｏｎ⁃ｓｔｅｒｏｉｄａｌ ａｎｔｉ⁃ｉｎｆｌａｍｍａｔｏｒｙ ５１

ＧＭＡ ｄｒｕｇｓ
ＵＦ ＨＡＰ ７０ ℃ ／ ２ ｈ ＳＰＥ ｇｒａｓｓ ｃａｒｐ ａｄｅｎｏｓｉｎｅ ｔｒｉｐｈｏｓｐｈａｔｅ ａｎｄ ｉｔｓ ５７

ｐｈｏｓｐｈｏｒｙｌａｔｅｄ ｍｅｔａｂｏｌｉｔｅｓ
ＥＤＭＡ ｐｏｒｏｕｓ ｏｒｇａｎｉｃ ｃａｇｅ ＡＩＢＮ／６０ ℃／１２ ｈ ＳＰＥ ｃｈｅｎｏｐｏｄｉｕｍ ｑｕｉｎｏａ ｗｉｌｌｄ ｅｃｄｙｓｔｅｒｏｉｄｓ ７１
３０ ℃ ／ ２．５
ＴＥＧＤＡ ｎａｎｏｄｉａｍｏｎｄ ｈ ｏｎ⁃ｌｉｎｅ ＳＰＥ ｅｄｉｂｌｅ ｏｉｌ β⁃ｓｉｔｏｓｔｅｒｏｌ ８４

ＵＶ： ｕｌｔｒａｖｉｏｌｅｔ； ＡＩＢＮ： ａｌｐｈａ⁃ａｚｏ⁃ｉｓｏｂｕｔｙｒｏｎｉｔｒｉｌｅ； ＡｕＮＰｓ： ｇｏｌｄ ｎａｎｏｐａｒｔｉｃｌｅｓ； ＮＭＡ： Ｎ⁃ｍｅｔｈｙｌｏｌａｃｒｙｌａｍｉｄｅ； ＵＦ： ｕｒｅａ⁃ｆ
ｏｒｍａｌｄｅ⁃ｈｙｄｅ； ＡｇＮＰｓ： ｓｉｌｖｅｒ ｎａｎｏｐａｒｔｉｃｌｅｓ； ＮＩＰＡＡｍ： Ｎ⁃ｉｓｏｐｒｏｐｙｌａｃｒｙｌａｍｉｄｅ； ＰＭＭＥ： ｐｏｌｙｍｅｒ ｍｏｎｏｌｉｔｈ ｍｉｃｒｏｅｘｔｒａｃｔｉｏ
ｎ； ＭＭＡ： ｍｅｔｈｙｌ ｍｅｔｈ⁃ａｃｒｙｌａｔｅ．

目前，对于纳米材料掺杂聚合物整体柱，通过简单
４ 结论与展望
掺杂、共聚合和原位修饰等合成方法，可以显著提高聚
合物整体柱的选择性和稳定性等性能，同时改
善其微观结构和吸附性能。 另一方面，纳米材料掺
杂聚合物整体柱萃取模式多种多样，涵盖ＳＰＥ、ＳＰ
ＭＥ、ＳＢＳＥ 和在线 ＳＰＥ 等多种样品前处理技术，
丰富了复杂样品的萃取模式，促进样品前处理领域的
发展。 此外，纳米材料掺杂聚合物整体柱已广泛
 第３ 期 李子凌，等：纳米材料掺杂聚合物整体柱的构筑及在前处理领域的应用 ·２３９
·
［１９］ Ｙｕ Ｈ， Ｌｉｕ Ｈ Ｙ， Ｙａｎｇ Ｃ Ｌ， ｅｔ ａｌ． Ａｎａｌ Ｍｅｔｈｏｄｓ， ２０２０， １
２：
６３８
应用于食品安全和环境卫生领域低浓度风险化合物的
［２０］ Ｍａｋｋｌｉａｎｇ Ｆ， Ｋａｎａｔｈａｒａｎａ Ｐ， Ｔｈａｖａｒｕｎｇｋｕｌ Ｐ， ｅｔ ａｌ．
前处理，同时，凭借纳米材料掺杂聚合物整体柱的表
面特异性和生物兼容性，使得该材料对生物样品和天
然药物中的目标化合物具有高选择性的富集能力。
然而，该类材料仍然会受到纳米材料性质和合成条件
的限制，例如对纳米材料的粒径、密度和合成的溶剂
等条件有一定要求；另外在材料的均匀性和稳定性方
面仍有待进一步改善。 充分发挥并挖掘纳米材料掺
杂聚合物整体柱的优势，在今后的研究中继续发展新
的纳米材料的种类，发展多样的合成方法，探索制备
和吸附分离机理并进一步拓展探索该类材料在生物医
药、食品分析和环境健康等领域的应用，对于卫生检
验、材料科学等多领域协同发展以及实际分析问题的
有效解决具有重要意义。
参考文献：

［１］ Ｈｊｅｒｔ é ｎ Ｓ， Ｌｉａｏ Ｊ Ｌ， Ｚｈａｎｇ Ｒ． Ｊ Ｃｈｒｏｍａｔｏｇｒ Ａ， １９８９， ４７３：

２７３
［２］ Ｌｙｎｃｈ Ｋ Ｂ， Ｒｅｎ Ｊ Ｔ， Ｂｅｃｋｎｅｒ Ｍ Ａ， ｅｔ ａｌ． Ａｎａｌ Ｃｈｉｍ Ａｃｔａ，
２０１９， １０４６： ４８
［３］ Ｅｅｌｔｉｎｋ Ｓ， Ｗｏｕｔｅｒｓ Ｓ， Ｄｏｒｅｓ⁃Ｓｏｕｓａ Ｊ Ｌ， ｅｔ ａｌ． Ｊ Ｃｈｒｏｍａｔｏｇｒ
Ａ， ２０１７， １４９８： ８
［４］ Ｙｉｎ Ｊ Ｆ， Ｗｅｉ Ｘ Ｙ， Ｙａｎｇ Ｇ Ｌ． Ｃｈｉｎｅｓｅ Ｊｏｕｒｎａｌ ｏｆ Ｃｈｒｏｍａｔｏｇ⁃
ｒａｐｈｙ， ２００７， ２５（２）： １４２
尹俊发， 魏晓奕， 杨更亮． 色谱， ２００７， ２５（２）： １４２
［５］ Ｐｅｎｇ Ｓ， Ｂａｉ Ｌ Ｇ， Ｗａｎｇ Ｌ Ｓ， ｅｔ ａｌ． Ａｎａｌ Ｂｉｏｃｈｅｍ， ２０２０，
５９１： １１３５５５
［６］ Ａｃｑｕａｈ Ｃ， Ｍｏｙ Ｃ Ｋ Ｓ， Ｄａｎｑｕａｈ Ｍ Ｋ， ｅｔ ａｌ． Ｊ Ｃｈｒｏｍａｔｏｇｒ
Ｂ， ２０１６， １０１５／ １０１６： １２１
［７］ Ｆｒｅｓｃｏ⁃Ｃａｌａ Ｂ， Ｃ á ｒｄｅｎａｓ Ｓ． Ａｎａｌ Ｃｈｉｍ Ａｃｔａ， ２０１８， １０３１： １５
［８］ Ｔｏｎｇ Ｓ Ｓ， Ｌｉｕ Ｓ Ｘ， Ｗａｎｇ Ｈ Ｑ， ｅｔ ａｌ． Ｃｈｒｏｍａｔｏｇｒａｐｈｉａ，
２０１４， ７７： ５
［９］ Ｒｉｂｅｉｒｏ Ｌ Ｆ， Ｍａｓｉｎｉ Ｊ Ｃ， Ｓｖｅｃ Ｆ． ＴｒＡＣ⁃Ｔｒｅｎｄｓ Ａｎａｌ Ｃｈｅｍ，
２０１９， １１８： ６０６
［１０］ Ｇａｎｅｗａｔｔａ Ｎ， Ｒａｓｓｉ Ｚ Ｅ． Ｅｌｅｃｔｒｏｐｈｏｒｅｓｉｓ， ２０１８， ３９： ５３
［１１］ Ｍａｙａ Ｆ， Ｐａｕｌｌ Ｂ． Ｊ Ｓｅｐ Ｓｃｉ， ２０１９， ４２： １５６４
［１２］ Ｋａｌｅｅｍ Ａ， Ａｚｍａｔ Ｍ， Ｓｈａｒｍａ Ａ， ｅｔ ａｌ． Ｆｏｏｄ Ｃｈｅｍ， ２０１９，
２７７： ６２４
［１３］ Ｄ í ａｚ⁃Á ｌｖａｒｅｚ Ｍ， Ｔｕｒｉｅｌ Ｅ， Ｍａｒｔ í ｎ⁃Ｅｓｔｅｂａｎ Ａ． Ａｎａｌ Ｃｈｉ
ｍ
Ａｃｔａ， ２０１９， １０４５： １１７
［１４］ Ｈｕ Ｘ Ｇ， Ｓｕｎ Ａ Ｑ， Ｍｕ Ｌ， ｅｔ ａｌ． ＴｒＡＣ⁃Ｔｒｅｎｄｓ Ａｎａｌ Ｃｈｅｍ，
２０１６， ８０： ４１６
［１５］ Ｊｕｎ Ｌ Ｙ， Ｍｕｂａｒａｋ Ｎ Ｍ， Ｙｅｅ Ｍ Ｊ， ｅｔ ａｌ． Ｊ Ｉｎｄ Ｅｎｇ Ｃｈｅｍ，
２０１８， ６７： １７５
［１６］ Ｌｉ Ｗ Ｋ， Ｓｈｉ Ｙ Ｐ． ＴｒＡＣ⁃Ｔｒｅｎｄｓ Ａｎａｌ Ｃｈｅｍ， ２０１９， １１８： ６５２
［１７］ Ｖａｌｃ á ｒｃｅｌ Ｍ， Ｓｉｍｏｎｅｔ Ｂ Ｍ， Ｃ á ｒｄｅｎａｓ Ｓ， ｅｔ ａｌ． Ａｎａｌ Ｂｉｏａｎ
ａｌ
Ｃｈｅｍ， ２００５， ３８２： １７８３
［１８］ Ｆｒｅｓｃｏ⁃Ｃａｌａ Ｂ， Ｍｏｍｐ ó⁃Ｒｏｓｅｌｌ ó Ｏ， Ｓｉｍ ó⁃Ａｌｆｏｎｓｏ Ｅ Ｆ， ｅ
ｔ
ａｌ． Ｍｉｃｒｏｃｈｉｍ Ａｃｔａ， ２０１８， １８５： １２７
 ［５１］ Ｌｉ Ｗ Ｘ， Ｈｕａｎｇ Ｌ， Ｇｕｏ Ｄ Ｄ， ｅｔ ａｌ． Ｊ Ｃｈｒｏｍａｔｏｇｒ
Ｔａｌａｎｔａ， ２０１８， １８４： ４２９ Ａ， ２０１８，１５７１： ７６
［２１］ Ｓａｔｔａｒ Ｔ． Ｔｏｐｉｃｓ Ｃｕｒｒ Ｃｈｅｍ， ２０１９， ３７７： １０
［２２］ Ｗａｎｇ Ｙ， Ｌｉ Ｓ Ｓ， Ｙａｎｇ Ｈ Ｙ， ｅｔ ａｌ． ＲＳＣ Ａｄｖ， ２０２０， １０：
１５３２８
［２３］ Ｔｏｎｇ Ｓ Ｓ， Ｌｉｕ Ｑ Ｗ， Ｌｉ Ｙ Ｃ， ｅｔ ａｌ． Ｊ Ｃｈｒｏｍａｔｏｇｒ Ａ， ２０１２，
１２５３： ２２

［２４］ Ｐｅｉ Ｍ， Ｓｈｉ Ｘ Ｌ， Ｗｕ Ｊ Ｙ， ｅｔ ａｌ． Ｔａｌａｎｔａ， ２０１９， １９１： ２５７

［２５］ Ｓｈｅｒｌａｌａ Ａ Ｉ Ａ， Ｒａｍａｎ Ａ Ａ Ａ， Ｂｅｌｌｏ Ｍ Ｍ， ｅｔ ａｌ． Ｃｈｅｍｏ⁃
ｓｐｈｅｒｅ， ２０１８， １９３： １００４
［２６］ Ｃｈｅｎ Ｘ Ｗ， Ｈａｉ Ｘ， Ｗａｎｇ Ｊ Ｈ． Ａｎａｌ Ｃｈｉｍ Ａｃｔａ， ２０１６， ９２２：
１
［２７］ Ｔｏｎｇ Ｓ Ｓ， Ｚｈｏｕ Ｘ， Ｚｈｏｕ Ｃ Ｈ， ｅｔ ａｌ． Ａｎａｌｙｓｔ， ２０１３， １３８：
１５４９

［２８］ Ｊｉｎｇ Ｔ Ｔ， Ｌｉ Ｆ， Ｃｈｅｎｇ Ｊ， ｅｔ ａｌ． Ｍｉｃｒｏｃｈｉｍ Ａｃｔａ， ２０１６， １８３：

５４３
［２９］ Ｃｈｅｎ Ｘ Ｌ， Ａｉ Ｌ Ｆ， Ｃａｏ Ｙ Ｑ， ｅｔ ａｌ． Ｆｏｏｄ Ａｎａｌ Ｍｅｔｈｏｄ，
２０１９， １２： ２７１
［３０］ Ｙｕａｎ Ｙ Ｐ， Ｚｈａｎｇ Ｈ Ｑ， Ｙａｎｇ Ｆ， ｅｔ ａｌ． Ｒｅｎｅｗ Ｓｕｓｔ Ｅｎｅｒｇ
Ｒｅｖ， ２０１６， ５４： ７６１
［３１］ Ｈｅｉｄａｒｉｎｅｊａｄ Ｚ， Ｄｅｈｇｈａｎｉ Ｍ Ｈ， Ｈｅｉｄａｒｉ Ｍ， ｅｔ ａｌ． Ｅｎｖｉｒｏｎ
Ｃｈｅｍ Ｌｅｔｔ， ２０２０， １８： ３９３
［３２］ Ｌｉｒｉｏ Ｓ， Ｆｕ Ｃ Ｗ， Ｌｉｎ Ｊ Ｙ， ｅｔ ａｌ． Ａｎａｌ Ｃｈｉｍ Ａｃｔａ， ２０１６，
９２７： ５５
［３３］ Ｋｕｏ Ｙ Ｃ， Ｈｅｉｓｈ Ｗ Ｑ， Ｈｕａｎｇ Ｈ Ｙ， ｅｔ ａｌ． Ｊ Ｃｈｒｏｍａｔｏｇｒ Ａ，
２０１８， １５３９： １２
［３４］ Ｚｈｕ Ｙ， Ｍｏｒｉｓａｔｏ Ｋ， Ｈａｓｅｇａｗａ Ｇ， ｅｔ ａｌ． Ｊ Ｓｅｐ Ｓｃｉ， ２０１５，
３８： ２８４１
Ｍｏｍｐ ó⁃Ｒｏｓｅｌｌ ó Ｏ， Ｖｅｒｇａｒａ⁃Ｂａｒｂｅｒ á ｎ Ｍ， Ｓｉｍ ó⁃Ａｌｆｏｎｓｏ
［３５］ Ｅ
Ｆ， ｅｔ ａｌ． Ｔａｌａｎｔａ， ２０２０， ２０９： １２０５６６
［３６］ Ｊｉａｎｇ Ｎ， Ｗａｎｇ Ｊ Ｂ， Ｌｉ Ｗ Ｂ， ｅｔ ａｌ． Ｊ Ｃｈｒｏｍａｔｏｇｒ Ａ， ２０１９，
１５８５： １９

［３７］ Ｃｈｅｎ Ｙ Ｌ， Ｘｉａ Ｌ， Ｌｉａｎｇ Ｒ Ｙ， ｅｔ ａｌ． ＴｒＡＣ⁃Ｔｒｅｎｄｓ Ａｎａｌ

Ｃｈｅｍ， ２０１９， １２０： １１５６５２
［３８］ Ｑｉ Ｒ Ｆ， Ｚｈｏｕ Ｘ， Ｌｉ Ｘ Ｑ， ｅｔ ａｌ． Ａｎａｌｙｓｔ， ２０１４， １３９： ６１６８
［３９］ Ｌｉｕ Ｄ， Ｍａ Ｊ Ｔ， Ｊｉｎ Ｙ， ｅｔ ａｌ． Ｊ Ｓｅｐ Ｓｃｉ， ２０１５， ３８： １３４
［４０］ Ｋｒｅｎｋｏｖａ Ｊ， Ｆｏｒｅｔ Ｆ． Ｊ Ｓｅｐ Ｓｃｉ， ２０１１， ３４： ２１０６
［４１］ Ｌｉ Ｗ Ｊ， Ｚｈｏｕ Ｘ， Ｙｅ Ｊ Ｊ， ｅｔ ａｌ． Ｊ Ｓｅｐ Ｓｃｉ， ２０１３， ３６： ３３３０
［４２］ Ｊｉａｏ Ｌ， Ｓｅｏｗ Ｊ Ｙ Ｒ， Ｓｋｉｎｎｅｒ Ｗ Ｓ， ｅｔ ａｌ． Ｍａｔｅｒ Ｔｏｄａｙ，
２０１９， ２７： ４３
［４３］ Ｌｉ Ｘ Ｊ， Ｍａ Ｗ， Ｌｉ Ｈ Ｍ， ｅｔ ａｌ． Ｃｏｏｒｄｉｎ Ｃｈｅｍ Ｒｅｖ， ２０１９，
３９７： １

［４４］ Ｒｏｃ í ｏ⁃Ｂａｕｔｉｓｔａ Ｐ， Ｔｅｒｍｏｐｏｌｉ Ｖ． Ｃｈｒｏｍａｔｏｇｒａｐｈｉａ， ２０１９，

８２： １１９１
［４５］ Ｌｙｕ Ｄ Ｙ， Ｙａｎｇ Ｃ Ｘ， Ｙａｎ Ｘ Ｐ． Ｊ Ｃｈｒｏｍａｔｏｇｒ Ａ， ２０１５， １３９３：
１
［４６］ Ｐａｎｇ Ｘ Ｙ， Ｌｉｕ Ｈ Ｙ， Ｙｕ Ｈ， ｅｔ ａｌ． Ｊ Ｃｈｒｏｍａｔｏｇｒ Ｂ， ２０１
９，
１１２５： １２１７１５
［４７］ Ｌｉｎ Ｃ Ｌ， Ｌｉｒｉｏ Ｓ， Ｃｈｅｎ Ｙ Ｔ， ｅｔ ａｌ． Ｃｈｅｍ Ｅｕｒ Ｊ， ２０１４， ２
０：
３３１７
［４８］ Ｗａｎｇ Ｚ Ｆ， Ｚｈａｎｇ Ｓ Ｎ， Ｃｈｅｎ Ｙ， ｅｔ ａｌ． Ｃｈｅｍ Ｓｏｃ Ｒｅｖ，
２０２０， ４９： ７０８
［４９］ Ｒｏｄｒ í ｇｕｅｚ⁃Ｓａｎ⁃Ｍｉｇｕｅｌ Ｄ， Ｍｏｎｔｏｒｏ Ｃ， Ｚａｍｏｒａ Ｆ． Ｃｈｅｍ Ｓｏｃ
Ｒｅｖ， ２０２０， ４９： ２２９１
［５０］ Ｗａｎｇ Ｈ Ｑ， Ｌｉ Ｚ， Ｆｅｎｇ Ｗ， ｅｔ ａｌ． Ｎｅｗ Ｊ Ｃｈｅｍ， ２０１７， ４
１：
１３０４３
 ·２４０· 色 谱 第３９卷
［５２］ Ｍａｌｌａｋｐｏｕｒ Ｓ， Ｎａｇｈｄｉ Ｍ． Ｐｒｏｇ Ｍａｔｅｒ Ｓｃｉ， ２０１８， ９７： ４０９ ＴｒＡＣ⁃Ｔｒｅｎｄｓ Ａｎａｌ Ｃｈｅｍ， ２０１６， ８０： ６５５
［５３］ Ｘｕ Ｐ Ｐ， Ｙａｏ Ｙ Ｃ， Ｓｈｅｎ Ｓ Ｃ， ｅｔ ａｌ． Ｃｈｉｎｅｓｅ Ｊ Ｃｈｅｍ Ｅｎｇ， ［６９］ Ａｌ⁃Ｒｉｆａｉ Ａ， Ａｑｅｌ Ａ， Ｗａｈｉｂｉ Ｌ Ａ， ｅｔ ａｌ． Ｊ Ｃｈｒｏｍａｔｏｇｒ Ａ，
６６７
２０１０， １８： ［７０］ ２０１８， １５３５： １７
［５４］ Ｎｉｕ Ｚ Ｌ， Ｚｈａｎｇ Ｗ Ｗ， Ｙｕ Ｃ Ｗ， ｅｔ ａｌ． ＴｒＡＣ⁃Ｔｒｅｎｄｓ Ａｎａｌ Ｌｉ Ｚ Ｌ， Ｌｉ Ｎ， Ｄｕ Ｌ， ｅｔ ａｌ． Ｊ Ｓｅｐ Ｓｃｉ， ２０１９， ４２： ３２３４
Ｃｈｅｍ， ２０１８， １０２： １２３ ［７１］ Ｗａｎｇ Ｈ Ｗ， Ｔａｎ Ｊ Ｎ， Ｓｈａｎｇ Ｘ Ｃ， ｅｔ ａｌ． Ｊ Ｃｈｒｏｍａｔｏｇｒ Ａ，
［５５］ Ｈａｂｒａｋｅｎ Ｗ， Ｈａｂｉｂｏｖｉｃ Ｐ， Ｅｐｐｌｅ Ｍ， ｅｔ ａｌ． Ｍａｔｅｒ Ｔｏｄａｙ， ［７２］ ２０１９， １５８３： ５５

２０１６， １９： ６９ Ｐ ł ｏｔｋａ⁃Ｗａｓｙｌｋａ Ｊ， Ｓｚｃｚｅｐａ ń ｓｋａ Ｎ， Ｇｕａｒｄｉａ Ｍ Ｄ Ｌ， ｅｔ ａｌ．

［５６］ Ｋｒｅｎｋｏｖａ Ｊ， Ｌａｃｈｅｒ Ｎ Ａ， Ｓｖｅｃ Ｆ． Ａｎａｌ Ｃｈｅｍ， ２０１０， ８２： ＴｒＡＣ⁃Ｔｒｅｎｄｓ Ａｎａｌ Ｃｈｅｍ， ２０１５， ７３： １９
Ｍｏｒｅｄａ⁃Ｐｉ ñ ｅｉｒｏ Ｊ， Ｍｏｒｅｄａ⁃Ｐｉ ñ ｅｉｒｏ
８３３５ ［７３］ Ａ． ＴｒＡＣ⁃Ｔｒｅｎｄｓ Ａｎａｌ
［５７］ Ｗａｎｇ Ｊ Ｂ， Ｌｉ Ｗ Ｂ， Ｘｉａｏ Ｊ Ｈ， ｅｔ ａｌ． Ｊ Ｃｈｒｏｍａｔｏｇｒ Ｂ， ２０１９， ［７４］ Ｃｈｅｍ， ２０１５， ７１： ２６５
１１２８： １２１７６９ Ｆｒｅｓｃｏ⁃Ｃａｌａ Ｂ， Ｃ á ｒｄｅｎａｓ Ｓ， Ｈｅｒｒｅｒｏ⁃Ｍａｒｔ í ｎｅｚ Ｊ Ｍ． Ｍｉｃｒｏ⁃
［５８］ Ｚｈａｎｇ Ｊ Ｌ， Ｃｈｅｎ Ｇ， Ｔｉａｎ Ｍ Ｍ， ｅｔ ａｌ． Ｔａｌａｎｔａ， ２０１３， １１５： ［７５］ ｃｈｉｍ Ａｃｔａ， ２０１７， １８４： １８６３
８０１ Ｌｉｒｉｏ Ｓ， Ｌｉｕ Ｗ Ｌ， Ｌｉｎ Ｃ Ｌ， ｅｔ ａｌ． Ｊ Ｃｈｒｏｍａｔｏｇｒ Ａ， ２０１６，
［５９］ Ｌｕｏ Ｘ Ｌ， Ｌｉ Ｇ Ｋ， Ｈｕ Ｙ Ｆ． Ｔａｌａｎｔａ， ２０１７， １６５： ３７７ ［７６］ １４２８： ２３６
［６０］ Ｇｉｅｓｂｅｒｓ Ｍ， Ｃａｒｒａｓｃｏ⁃Ｃｏｒｒｅａ Ｅ Ｊ， Ｓｉｍ ó⁃Ａｌｆｏｎｓｏ Ｅ Ｆ， ｅｔ ａｌ． Ｈｅ Ｍ， Ｃｈｅｎ Ｂ Ｂ， Ｈｕ Ｂ． Ａｎａｌ Ｂｉｏａｎａｌ Ｃｈｅｍ， ２０１４， ４０６：
Ｍｉｃｒｏｃｈｉｍ Ａｃｔａ， ２０１９， １８６： ７５９ ［７７］ ２００１
［６１］ Ｌｉｕ Ｌ Ｈ， Ｙａｎｇ Ｃ Ｘ， Ｙａｎ Ｘ Ｐ． Ｊ Ｃｈｒｏｍａｔｏｇｒ Ａ， ２０１７， １４７９： Ｄａｖｉｄ Ｆ， Ｏｃｈｉａｉ Ｎ， Ｓａｎｄｒａ Ｐ． ＴｒＡＣ⁃Ｔｒｅｎｄｓ Ａｎａｌ Ｃｈｅｍ，
１３７ ［７８］ ２０１９， １１２： １０２
［６２］ Ｚｈａｎｇ Ａ Ｚ， Ｙｅ Ｆ Ｇ， Ｌｕ Ｊ Ｙ， ｅｔ ａｌ． Ｃｈｉｎｅｓｅ Ｊｏｕｒｎａｌ ｏｆ Ａｎａ⁃ Ｙｏｕ Ｌ Ｎ， Ｈｅ Ｍ， Ｃｈｅｎ Ｂ Ｂ， ｅｔ ａｌ． Ｊ Ｃｈｒｏｍａｔｏｇｒ Ａ， ２０１７，
ｌｙｔｉｃａｌ Ｃｈｅｍｉｓｔｒｙ， ２０１１， ３９（８）： １２４７ ［７９］ １５２４： ５７
张爱珠， 叶芳贵， 陆俊宇， 等． 分析化学， ２０１１， ３９（８）： １２４７ Ｙａｎｇ Ｊ Ｈ， Ｃｕｉ Ｃ Ｘ， Ｑｕ Ｌ Ｂ， ｅｔ ａｌ． Ｍｉｃｒｏｃｈｅｍ Ｊ， ２０１８，
［６３］ Ｆｏｘ Ｋ， Ｔｒａｎ Ｐ Ａ， Ｔｒａｎ Ｎ． Ｃｈｅｍ Ｐｈｙｓ Ｃｈｅｍ， ２０１２， １３： ［８０］ １４１： ３６９
２４９５ Ｍａｃｉｅｌ Ｅ Ｖ Ｓ， Ｔｏｆｆｏｌｉ Ａ Ｌ Ｄ， Ｌａｎ ç ａｓ Ｆ Ｍ． Ｊ Ｓｅｐ Ｓｃｉ， ２０１９，
［６４］ Ｘｉａ Ｌ， Ｌｉ Ｙ Ｘ， Ｌｉｕ Ｙ Ｌ， ｅｔ ａｌ． Ｊ Ｓｅｐ Ｓｃｉ， ２０２０， ４３： １８９ ［８１］ ４２： ２５８
［６５］ Ｂｕｒａｔｏ Ｊ Ｓ Ｄ Ｓ， Ｍｅｄｉｎａ Ｄ Ａ Ｖ， Ｔｏｆｆｏｌｉ Ａ Ｌ Ｄ， ｅｔ ａｌ． Ｊ Ｓｅｐ Ｌｉａｎｇ Ｙ Ｓ， Ｚｈｏｕ Ｔ． Ｊ Ｓｅｐ Ｓｃｉ， ２０１９， ４２： ２２６
Ｓｃｉ， ２０２０， ４３： ２０２ ［８２］ Ｙａｎｇ Ｃ Ｘ， Ｙａｎｇ Ｘ Ｑ， Ｙａｎ Ｘ Ｐ． Ｃｈｉｎｅｓｅ Ｊｏｕｒｎａｌ ｏｆ Ｃｈｒｏｍａ⁃
［６６］ Ｈａｎｓｅｎ Ｆ Ａ， Ｐｅｄｅｒｓｅｎ⁃Ｂｊｅｒｇａａｒｄ Ｓ． Ａｎａｌ Ｃｈｅｍ， ２０２０， ９２： ｔｏｇｒａｐｈｙ， ２０１９， ３７（８）： ８２４
２ Ｅ， Ｇ ó ｍｅｚ⁃Ｒ í ｏｓ 杨成雄， 杨雪清， 严秀平． 色谱， ２０１９， ３７（８）： ８２４
［６７］ Ｒｅｙｅｓ⁃Ｇａｒｃ é ｓ Ｎ， Ｇｉｏｎｆｒｉｄｄｏ Ｇ Ａ， ｅｔ ａｌ． ［８３］ Ｃｕｉ Ｂ Ｊ， Ｇｕｏ Ｂ， Ｗａｎｇ Ｈ Ｍ， ｅｔ ａｌ． Ｔａｌａｎｔａ， ２０１８， １８６： ２００
Ａｎａｌ Ｃｈｅｍ， ２０１８， ９０： ３０２ Ｖ， ［８４］ Ｃｕｉ Ｂ Ｊ， Ｌｉｕ Ｈ Ｙ， Ｙｕ Ｈ， ｅｔ ａｌ． Ｆｏｏｄ Ａｎａｌ Ｍｅｔｈｏｄ， ２０１９，

［６８］ Ａｎｄｒａｄｅ⁃Ｅｉｒｏａ Ａ， Ｃａｎｌｅ Ｍ， Ｌｅｒｏｙ⁃Ｃａｎｃｅｌｌｉｅｒｉ ｅｔ ａｌ． １２： ６９７