Добавил:
Sekretar
kiopkiopkiop18@yandex.ru
t.me/Prokururor I Вовсе не секретарь, но почту проверяю
Опубликованный материал нарушает ваши авторские права? Сообщите нам.
Вуз:
Предмет:
Файл:Ординатура / Хирургия / Библиотека им академика М.И. Перельмана / Книга_5936_Библиотеки_им_академика_М_И_Перельмана
.pdf
118 Manoj Kumar Banjare et al.
https://t.me/medicina_free
Table 6.3 (continued)
Detection method Sample Detection limit Linear range References
Years
[]
Ion
Collaborative
detection by
H
O
. µM (colorimetric
method)
– Su et al.
colorimetric and
fluorescence
Methods . μM (fluorescence
method)
– – . µM . µM–. mM Yang et al. b
– Glucose . μM (colorimetric
– Su et al.
method fluorescence
method)
– Xanthine . μM (colorimetric
– Su et al.
method)
. μM (fluorescence
method)
– Hydroquinone
Q)
(H
μM .– mM Ren et al.
– mM
– Cholesterol . µM . µM Yang et al. b
. mM
Collaborative
detection by
Uric acid – μM
(colorimetric method)
– Wang et al.
colorimetric and
SERS
methods .– μM
SERS method
– Glucose –
– Gan et al.
× M
Double emission
carbon spot
OPhenylenediamine
. μM – Mathivanan
et al.
detection
– H
O
. μM – Mathivanan
et al.
– Hydroquinone
(H
Q)
. μM .– μM Wang et al.
Chapter 6 Carbon dots in nanozymes 119
https://t.me/medicina_free
6.3.6 Detection of glucose and glutathione
As was previously noted, H2O2is a crucial signalling molecule in pathological and metabolic processes, particularly in glucose metabolism. In the absence of oxygen, glucose
can be catalysed to create gluconolactone and H
(GSH) can be measured indirectly by checking the amount of H
leased by enzymes (184, 189, 190, 203).
. As a result, glucose and glutathione
2O2
that has been re-
2O2
6.3.7 Detection of proteins
The tailored immune sorbent assay to find protein molecules has also used carbon
nanozymes. The first method for the extremely sensitive detection of carcino embryonic antigen was created by [141].
6.3.8 Detection of nucleic acids
Both applications in nucleic acid detection and uses for sensitive nanozyme assays
have been discovered by researchers.
6.3.9 Detection of cancer cells
Recently, carbon nanozymes have become an intriguing cancer cell monitoring and
detection assay [141].
6.3.10 Bio-sensing of CD-based nanozymes
Nanozymes have gained popularity as an ideal and crucial component for biosensors
since they are less expensive, more stable, and easier to synthesize than protein enzymes.
Potential biosensors have been investigated using MoS
nanoparticles, AuNP@MoS
with a variety of enzymatic activity [134].
QD gold nanoparticles, and other inorganic nanomaterials
2
nanoribbons, ferromagnetic
2
6.3.11 The biosensor colorimetric
The cholesterol oxidase and cascade colorimetric biosensor demonstrated excellent selectivity and high sensitivity to the target. The detection cut-off was reduced to 7 mM (219).
120 Manoj Kumar Banjare et al.
https://t.me/medicina_free
6.3.12 Sensors electrochemical of CD-based nanozymes
Electrochemical sensors have several advantages, including linear output, good resolution, low power consumption, repeatability, and precision. A contemporary topic is
the application of nanozymes based on CDs in electrochemical sensors [142–146].
6.3.13 The high catalytic activity of CD-based nanozymes
The copper based oxidase, superoxide oxidase, peroxidase, and catalase reactions are
basic nanozyme catalytic reactions. Despite the variety and vast range of catalytic
abilities displayed by natural enzymes, c reating nanozymes for novel enzyme reactions is incredibly challenging [135]. However, a 200 °C high-temperature alkaline solution with a pH of 8.5 is the ideal reaction environment for this nanozyme. Its
employment in biological systems is greatly constrained by thes e extreme reaction
conditions [147–151].
6.3.14 Environmental application of CD-based nanozymes
Similar to real enzymes, environmental conditions such as pH levels, ionic strengths, temperatures, and light have a significant impact on the catalytic activity of carbon nanozymes [137]. Additionally, beyond 60 °C, HRP’s catalytic activity was almost completely
suppressed while N-GQDs continued to exh ibit strong catalytic capabilities. Carbon
nanoparticles’ distinctive optical features also make carbon nanozymes the most lightsensitive compound. Carbon nanoparticles’ enzyme-like activity can thus be controlled
by light [160].
6.3.15 Oxidase/laccase-like activity
Nanozymes have a number of benefits over natural oxidases in terms of use, production,
and catalytic activity. Due to their capacity to catalyse oxidation events without the presence
, several oxidase-like nanozymes have been identified. High catalytic activity has
of H
2O2
been observed for metal nanoparticles, nanocomposite carbon materials, and MOx [56].
Shamsipur et al. [161] studied carbon quantum dots (CD-1) with peroxidase activity
to track GSH levels in human blood. Na
and it was heated for two hours at 40 °C under argon (Figure 6.4). When TMB is added to
TMBox, CD-1, a peroxidase, can be used to catalyse the conversion of TMB to H
changes the colour of the substance from colourless to blue. H
largely neutral reactions lacking CD-1. At wavelengths 370, 450, and 653, three different
emission peaks were seen when CD-1 was introduced [152–156].
EDTA.2H2O was used as the starting material,
2
,which
2O2
and TMB I and II had
2O2
High
https://t.me/medicina_free
catalytic
activity and
Environmental
application
Chapter 6 Carbon dots in nanozymes 121
Biomedical
Biomedicine
Bio-sensing
and Sensors
electro
chemical
Detection of
cancer cells
proteins,
nucleic
acids, and
Application
of CDs-
based
nanozymes
Detection of
glucose and
glutathione
Detection of
O
2andH2O2
Bio-imaging
and bio-
detection
Figure 6.4: Applications of CDs.
To detect H2O2at the nanomolar level, Yousefinejad et al. [162] created new Fe-CD-2
as a peroxidase mimic. To create Fe-CD-2, CD-2, and Fe
NPs were combined in an
3O4
acidic environment at a 4:1 ratio, and CD-2 was created utilizing carbon soot and nitric
acid as precursors (Figure 6.5). Fe-CD-2 was identified by transmission electron microscopy pictures as a hemisphere with a size of roughly 10 nm. With H
,Fe-CD-2wasable
2O2
to catalyse the oxidation of TMB to TMBox, which resulted in a colour shift from colourless to blue. Under the same circumstances, TMBox displayed more absorbance with FeCD-2 than with CD-2 and Fe
relationship with the H
2O2
and Fe-CD-2 to 1 mmol L
NPs alone. The absorbance displayed a remarkable linear
3O4
concentration starting at 10 nmol L–1inthepresenceofTMB
–1
, with a remarkably low detection threshold of just 1 nmol L–1.
To detect chromium ions [Cr(III)], Li et al. [163] reported copper-doped CDs (CD-7)
as a peroxidase mimic. Na
create CD-7 (Figure 6.7). OPD was oxidized in DAP in the presence of CD-7 by H
[Cu(EDTA)] was cooked at 27 °C for 2 h in a tube furnace to
2
2O2
which released yellow fluorescence at 564 nm under excitation of 421 nm. A new absorption peak at 400 nm formed once Cr(III) was introduced, and the produced DAP’s
fluorescence intensity rapidly reduced (Table 6.4).
,
Table 6.4: Kinetic parameters of recent studies on CDs, doped-CDs, and CD-based hybrid nanozymes with oxidase/laccase-like activity and their application in
https://t.me/medicina_free
detection systems.
CDs/CD-hybrid Enzyme-like Substrates Michaelis–Menten parameters Application References
K
+
Ce
-CDs OXidase TMB . (pH ),
. (pH )
(mM) V
m
(–Ms–) Detection Linear range (μM) LOD (μM)
max
. (pH ) and
NA NA NA Li et al. []
. (pH )
Cu-CDs Laccase TMB NA NA Hydroquinone ,–, Ren et al. []
+
Ce
-GQDs OX idase OPD NA NA Aledronate Sodium .–.
. Xia et al. []
.–
-CDs OXidase TMB NA NA Glutathione .– . Cao et al. []
MnO
CD-Cu
O
Ag/His-GQD O
-CQDs OXidase OPD NA NA -Mercaptopurine .– . An et al. []
MnO
Mn-CDs O
OXidase TMB . . Li et al. []
Xidase TMB .. D-Penicillamine .–. . Dan et al. []
Xidase TMB NA NA Ascorbic acid .–.. Zhuo et al. []
Note: NR represents not reported.
122 Manoj Kumar Banjare et al.
Chapter 6 Carbon dots in nanozymes 123
https://t.me/medicina_free
(B)
0.20
(A)
+
Na
O
–
O
O
–
O
N
–
Na
O
O
Na2EDTA . 2H2O
O
400 ºC, 2 h
N
–
O
+
Argon flow
H2O
CDs–1
H2NH2NHN
2
TMB IITMB I
TMB
2
GSH
TMB
ox
+
NH
3
0.18
0.16
0.14
0.12
0.10
0.08
Absorbance
0.06
0.04
0.02
0.00
a
[GSH]
h
600
Wavelength (nm)
Figure 6.5: (A) The method of making CD-1 and the theory behind how it reacts with TMB I and II in the
presence of H
before reacting with GSH. (B) TMBox absorption as GSH increases (copying is permitted
2O2
[161]. Copyright 2014, Elsevier).
800750700650550500
Figure 6.6: (A) The Fe-CD-2 synthesis pathway and Fe-CD-2 catalysed TMB oxidation by H2O2. (B) TMBox
absorbance at 653 nm as a function of H
Copyright 2017, Elsevier).
A nanozyme (CD-15) that may release DNAzyme to boost catalytic efficiency in the
+
presence of K
was described by Li et al. [164] in detail. Corn starch and ethylenediamine were microwaved at 14 °C for 10 min to create CD-15 (Figure 6.8). Apt-CDs15 decreased CD-15’s fluorescence when it was coupled with an aptamer (Apt), which was
explained by the inhibition of catalytic activity. Apt-CD-15 developed hemin-containing
DNAzyme (HM) to increase CD-15’s catalytic activity when K
, CD-15 and DNAzyme accelerated the production of TMBox, which displayed a
of H
2O2
concentration (mM: mmol L–1) (copying is permitted [162].
2O2
+
is present. In the presence
124 Manoj Kumar Banjare et al.
https://t.me/medicina_free
(A)
(B)
O
O
O
–
1000
800
600
400
+
–
Na
O
N
+
Na
Cu
O
2+
N
–
O
270 ºC, 2 h
–
O
O
0
CDs-7
OPD
H
2O2
DAP
high fluorescent
Cr
IFE effect
3+
nonfluorescent
Intensity (a.u.)
200
0
150 µ mol L
500
550 650600
-1
700
750450
Wavelength (nm)
Figure 6.7: (A) Mechanism of CD-7’s synthesis and detection with peroxidase activity for Cr (III).
(B) Fluorescence intensity of DAP as Cr(III) concentration is increased (copying is permitted [163].
Copyright 2020, Elsevier).
fluorescence signal at 403 nm and an absorption band at 563 nm. As the concentration
+
of Apt-CD-15 with K
was raised, the fluorescence intensity of TMBox gradually rose
[157–159].
Novel copper-doped CDs (CD-18) were described by Ren et al. [165] as an oxi dase
mimic for tracking hydroquinone (H
Q) levels. Cu (NO3)2andsodiumsaltofpoly
2
(methacrylic acid) were used as raw materials in the hydrothermal process to create
CD-18 (Figure 6.9). In a wide pH range, CD-18 showed outstanding photostability and
stability and released blue fluorescence at 460 nm (3.0–13.5). The colourless compound
p-phenylenediamine (PPD) turned brown after 30 min after being added to CD-18, which
promoted the oxidation of PPD and produced a distinct absorption peak at 495 nm. The
ideal pH was 8.5, and CD-18 demonstrated greater temperature stability than laccase. PPD
and the oxidation product of PPD on the surfaceofCD-18couldberemovedbyflocculation between polyacrylamide (PAM+) and CD-18 when PAM+ was applied. Additionally,
CD-18 responded to H
In carbonate buffer (pH 9.2), the relative fluorescence quenching (I/I
markable linear relationship with the H
The fluorescence intensity at 460 nm decreased with increasing H
detection limit was 1 mmol L
tion Agency’s3mmolL
Q by changing its hue from colourless to yellow in less than 10 min.
2
)demonstratedare-
0
Q concentration in the range of 0.05–2 mmol L–1.
2
Q concentration. The
–1
,whichissubstantiallylessthan the Environmental Protec-
–1
permissible thresholds. Additionally, CD-18 responded to H2Q
2
by changing its hue from colourless to yellow in less than 10 min. In carbonate buffer
(pH 9.2), the relative fluorescence quenching (I/I
) demonstrated a remarkable linear
0
Chapter 6 Carbon dots in nanozymes 125
https://t.me/medicina_free
Figure 6.8: (A) The CD-15 synthesis method. (B) The process by which TMB is oxidized when Apt-CD-15
+
are present. (C) Fluorescence intensity of the TMBox as K+concentration increases (reproduced
and K
with permission [164]. Copyright 2020, Elsevier).
relationship with the H2Q concentration in the range of 0.05–2mmolL–1. The fluorescence intensity at 460 nm decreased with increasing H
–1
limit was 1 mmol L
Agency’s3mmolL
2
2
NH
Figure 6.9: (A) Schematic representation of CD-18 reacting to PPD. (B) Variation in CD-18’s fluorescence
intensity as H
permission [165]. Copyright 2018, Royal Society of Chemistry).
Q concentration (mM: mmol L–1) was increased in the carbonate buffe (copied with
2
, which is substantially less than the Environmental Protection
–1
permissible thresholds.
(B)(A)
NHNH
CDs-18
Cu
NH
Q concentration. The detection
2
1000
800
600
400
200
Fluorescence intensity (a.u.)
0
400 550 600
500450
Wavelength (nm)
HQ
5 mM
126 Manoj Kumar Banjare et al.
https://t.me/medicina_free
Li et al. [166] reported CD-21 with the Ce3+-driven pH-dependent photo-oxidation
feature. Under visible light, in the presence of oxygen, CD-21 converted colourless
TMB to blue TMBox at the natural pH (Figure 6.10). With rising pH, the K
3+
CD-21-Ce
3+
Ce
under acidic conditions by the 1O
trast, because the Ce
condition, 1O
oxidized Ce
+EDTA• 2Na decreased more than that of CDs-21, indicating that CD-21-
+EDTA•2Na has a higher affinity for TMB. TMB was converted to TMBox
2
3+
/Ce4+potential diminishes with rising pH, under the neutral pH
, which was photo-generated by CD-21-Ce3++ EDTA 2Na under illumination,
2
3+
to Ce4+and TMB was then further oxidized by Ce4+. Additionally, the main
produced from CD-21 in the presence of light. In con-
value of
m
factor in the oxidation of TMB in a pH-neutral environment was the oxidation product
4+
which was stabilized by EDTA.2Na to stop the production of cerium hydroxide.
Ce
Figure 6.10: (A) The process by which CD-21-Ce3++ EDTA 2Na oxidizes TMB in ambient light. (B) Variations
in TMB’s colour under various circumstances (copied with permission [166]. Copyright 2020, Elsevier).
To scavenge for free radicals, Dehvari et al. [167] created peroxidase-active CDs (CD-25).
By employing citric acid trisodium salt, N-acetyl-
S as starting ingredients, CD-25 was created using the microwave hydrothermal
Na
2
technique (Figure 6.11). Because the oxidation of TMB was catalysed by the production
of OH, the solution changed from colourless to blue when TMB was treated with H
and Fe2+. The distinctive absorption peak of ox-TMB also developed at 652 nm. The elimination of OH by CD-25 was the reason for the system’s considerable decrease in
L-cysteine, manganese acetate, and
2O2
Chapter 6 Carbon dots in nanozymes 127
https://t.me/medicina_free
absorbance at 652 nm when CD-25 was added. Furthermore, CD-25 had a significant
–1
ability for scavenging reactive nitrogen species; at 100 mg mL
, CD-25 demonstrated a
98% scavenging effect for ONOO. As soon as the CD-25 surface was in contact with hyaluronic acid (HA), the increase in surface negative functional groups significantly increased the water solubility of HA-CD-25.
Figure 6.11: (A) The method by which HA-CD-25 is synthesized and the associated mechanism for
lowering ROS. (B) Photographs of B
(mM: mmol L–1), and HA-CD-25 (reproduced with permission [167]. Copyright 2020, Elsevier).
cells after they had been exposed to DCFH-DA, H2O
16F1
2
6.4 Current issues and proposed fixes
However, there are still a number of obstacles to be overcome:
1. The link between structure and activity has to be better understood. As was previ-
ously mentioned, a number of carbon nanostructures have enzyme catalytic activity. However, the structure–activity relationship does not appear to follow any
overall trend. Each system displays unique characteristics when the catalytic ability is evaluated, and these characteristics are explained by particular mechanisms. The hypothesized processes are typically diverse, which make it difficult to
develop CDs nanozymes in an efficient manner.
2. A number of variables, including the raw materials used to make CDs, influence
the activity of nanozymes.
3. Although CDs are biocompatible, a thorough a ssessment of their biosafety and
biocompatibility should be conducted. Even when doped with additional elements
like nitrogen, CDs often exhibit no cytotoxicity or very little cytotoxicity [80].
Соседние файлы в папке Библиотека им академика М.И. Перельмана