NE 52-QQ57

Antagonism of GPR4 with NE 52-QQ57 and the Suppression of AGE- Induced Degradation of Type II Collagen in Human Chondrocytes
Haochuan Liu, Yulong Liu, and Bing Chen*
Cite This: https://dx.doi.org/10.1021/acs.chemrestox.0c00111
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ABSTRACT: Osteoarthritis (OA) is a common degenerative joint disease for
which an effective therapeutic strategy has not yet been established. AGEs are
widely recognized as a contributor to OA pathogenesis. GPR4, a recently
discovered proton-sensing transmembrane receptor, has been shown to possess a
wide range of physiological functions. However, the potential role of this receptor
in chondrocytes and the pathogenesis of OA is unclear. In the present study, we
investigated the potential of GPR4 to modulate the effects of advanced glycation
end products (AGEs) in SW1353 human chondrocytes. First, we demonstrate
that GPR4 is fairly expressed in SW1353 chondrocytes and that exposure to AGEs
increases the expression of this transmembrane receptor. Second, we found that
antagonism of GPR4 with NE 52-QQ57 significantly inhibited the AGE-induced
increased expression of several key inflammatory cytokines and signaling
molecules, including tumor necrosis factor-α (TNF-α), interleukin (IL)-1β, IL-
6
, inducible nitric oxide synthase (iNOS), nitric oxide (NO), cyclooxygenase 2
(COX2), and prostaglandin E (PGE ). We also found that antagonisn of GPR4 had a remarkable ability to rescue type II collagen
2
2
from AGE-induced degradation by inhibiting the expression of matrix metalloproteinase (MMP)-3 and MMP-13. As a key pro-
inflammatory signaling pathway, we further tested the effect of GPR4 antagonism on the activation of nuclear factor-κB (NF-κB) and
found that NF-κB activation was indeed suppressed, thereby indicating that the NF-κB signaling pathway may mediate the effects of
GPR4 antagonism described above. These findings provide a basis for further research into the role of GPR4 -mediated signaling in
OA.
1
. INTRODUCTION
In recent years, the pivotal role of inflammation in OA has
received increasing attention. Tumor necrosis factor-α (TNF-
α) is a major cytokine involved in AGE-mediated inflamma-
tion. AGE-induced dysfunctional chondrocytes produce high
levels of TNF-α and interleukin (IL)-1β, which triggers the
release of IL-6 and ECM-degrading proteoglycans, such as
matrix metalloproteinase (MMP)-3 and MMP-13, while
Osteoarthritis (OA) is an increasingly common joint disease
characterized by excessive destruction of the articular
extracellular matrix (ECM). Chondrocytes are the main cell
type found in articular cartilage and serve a dual regulatory role
by synthesizing new cartilage tissue and destroying old or
injured tissue. However, in OA, chondrocyte dysfunction leads
to excessive degradation of the ECM and irreversible joint
damage. Factors involved in the initiation of OA include
obesity, gender, genetics, mechanical injury, diet, and most
significantly, age. Advanced glycation end-products (AGEs)
inhibiting the synthesis of aggrecan and type II collagen, the
1
,2
11,12
main structural components of the articular ECM.
Inhibiting the degradation of type II collagen, which has a
particularly slow rate of turnover, is an attractive treatment
3
,4
result from the process of nonenzymatic glycation involving
reducing sugars, amino acids, lipids, and DNA, and accumulate
in tissues over time. The accumulation of AGEs has been
associated with a wide range of intractable and degenerative
diseases, including diabetes, chronic kidney disease, Alz-
target. TNF-α and IL-6 are associated with age-related
systemic inflammation, which is recognized as a major
contributor to OA and other age-related pathologies. IL-6 is
strongly correlated with reduced physical function and the
heimer’s disease, and OA, among others.5 In chondrocytes,
AGEs induce the expression of proinflammatory cytokines,
secretion of degradative enzymes, and activation cellular
−8
Received: March 24, 2020
Published: May 6, 2020
signaling pathways, including the so-called “master switch” of
9
inflammation, nuclear factor-κB (NF-κB). Recent research has
demonstrated that inhibiting the effects of AGEs may be a
method to slow or halt the progression of OA.10
©
XXXX American Chemical Society
https://dx.doi.org/10.1021/acs.chemrestox.0c00111
A
Chem. Res. Toxicol. XXXX, XXX, XXX−XXX

Chemical Research in Toxicology
pubs.acs.org/crt
Article
development of degenerative diseases, and increased serum
levels of IL-6 are viewed as a biomarker for the pathogenesis of
OA. Additionally, IL-1β induces the expression of inducible
2.3. Western Blot Analysis. After the indicated treatment, RIPA
buffer supplemented with protease inhibitor cocktail was used to lyse
the chondrocytes. A total of 20 μg of cell lysates was loaded onto 4−
1
3
2
0% precasted poly acrylamide gel electrophoresis (PAGE) gel and
nitric oxide synthase (iNOS), which mediates nitric oxide
(NO) production. NO is an important proinflammatory
mediator that contributes to the pathogenesis of OA by
driving the destruction of type II collagen.14 Prostaglandin E2
(PGE2) is a product of arachidonic acid metabolism that has
been shown to promote cartilage degradation, bone remodel-
ing, and cartilage turnover in OA.15 Numerous studies have
focused on reducing the expression of these cytokines and
signaling molecules to hinder cartilage destruction as a
potential treatment method for OA. However, safe and
effective treatment targets remain to be identified.
the proteins were separated according to size. The separated protein
mixture was then transferred onto polyvinylidene fluoride (PVDF)
membranes. The membranes were blotted against the primary
°
antibodies overnight at 4 C and, after washing 3 times, were
incubated with corresponding HRP-conjugated secondary antibodies
for 1 h at room temperature. HRP substrate and ImageJ software were
used to detect and visualize the resulting protein signals.
2
.4. ELISA. The protein secretions of the target genes were
measured using enzyme-linked immunosorbent assay (ELISA).
Briefly, the supernatants were collected from the culture medium by
centrifugation at 1000 rpm for 10 min. Commercial ELISA kits for
TNF-α, IL-1β, IL-6, PGE , MMP-3, and MMP-13 were purchased
2
G protein-coupled receptors (GPCRs) have been receiving
increasing attention for their diverse range of physiological
roles. GPR4 is a proton-sensing transmembrane receptor that
is activated in response to low pH levels. Antagonism of this
receptor has been shown to reduce intestinal inflammation in
from R&D Systems and used in accordance with the manufacturer’s
instructions. The results are presented as fold-changes.
2.5. Determination of NO. We performed a cellular staining
experiment using the cell-permeable fluorescent probe 4-amino-5-
methylamino-2′,7′-difluorofluorescein (DAF-FM DA; Thermo Fisher
Scientific, U.S.A.) to determine the intracellular production of NO.
Briefly, SW1353 chondrocytes were grown to full confluence on a 96-
well plate and then incubated with 5 μM DAF-FM DA for 10 min.
The fluorescent signals were visualized with excitation at 495 nm and
emission detection at 515 nm via fluorescence microscopy.
1
6
17
mice and modulate nociception and angiogenesis, which
may be of use in the treatment of OA. Interestingly, recent
research has shown that activation of GPR4 by acidosis can
alter cytoskeletal phenotype and cell migration.18 However,
there is little known regarding the role of GPR4 in cartilage
and particularly, in the pathogenesis of OA. In the present
study, we identified that GPR4 is expressed in chondrocytes
and increased upon exposure to AGEs. Antagonism of GPR4
with its antagonist NE 52-QQ57 (chemical name 2-(4-((2-
ethyl-5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-yl)methyl)-
phenyl)-5-(piperidin-4-yl)-1,3,4-oxadiazole) significantly re-
duced the AGE-induced expression of various inflammatory
mediators and degradative enzymes, thereby demonstrating a
potential role for GPR4 antagonism in the prevention and
2.6. NF-κB Luciferase Reporter Assay.
Promoter luciferase
activity was measured to evaluate the transcriptional activity of NF-
κB. Briefly, the cells were cotransfected with NF-κB promoter
(Beyotime Biotechnology, China) and pRL-TK firefly promoter
(Promega, U.S.A.) plasmids using Lipofectamine 2000 reagent
(Thermo Fisher Scientific, U.S.A.). After the indicated treatment,
the total cell lysates were collected and a dual luciferase reporter assay
(Promega, U.S.A.) was used to measure the dual luciferase activity of
renilla and NF-κB. The relative luciferase activity was calculated by
normalizing the firefly to the renilla luciferase activity.
2.7. Statistical Analysis. The experimental data from all
procedures are presented as means ±
SEM. One-way analysis of
variance (ANOVA) followed by Bonferroni’s posthoc test were used
to determine the statistical significance of differences. It was calculated
that a P value of <0.05 represented a statistically significant difference. 1 9 treatment of OA. 2 . MATERIALS AND METHODS 2 .1. Cell Culture and Treatment. Human chondrosarcoma cell line SW1353 chondrocytes purchased from the American Type Culture Collection (ATCC) were used in all experiments. Human umbilical vein endothelial cells (HUVECs) from ATCC were used as a positive control in the GPR4 expression experiment. The cells were stored in a humidified incubator with 95% oxygen and 5% CO at 37 3. RESULTS 3 .1. GPR4 as Expressed in Human Chondrocytes and Increased by AGEs. We began by confirming that GPR4 is expressed in SW1353 chondrocytes. HUVECs have been shown to express GPR420 and were used as a positive control. As shown in Figure 1A,B, GPR4 is indeed expressed at both the mRNA and protein levels. Next, we determined whether the expression of GPR4 is responsive to AGE treatment. The results show that, upon stimulation with 50, 100, and 200 μg/ mL AGEs, the expression of GPR4 increased 1.9-, 2.6-, and 2 ° C and maintained in Leibovitz’s L-15 medium supplemented with 1 6 0% FBS and 1% penicillin/streptomycin. The cells were seeded into -well plates and grown to full confluence. For AGE treatment experiments, the AGE treatment reagent was freshly prepared in 150 mg/mL stock solution. The confluent SW1353 cells were then treated with 50, 100, and 150 μg/mL AGEs for 24 h to determine the AGE- induced expression of GPR4. For subsequent experiments, the cells were stimulated with 100 μg/mL AGEs for 24 h in the presence or absence of the GPR4 antagonist NE 52-QQ57 (0.5 and 1 μM; Novartis, Basal, Switzerland). To measure the activity of NF-κB, the cells were stimulated with AGEs for 2 h in the presence or absence of NE 52-QQ57. 3 .1-fold at the mRNA level (Figure 2A) and 1.8-, 2.4-, and 2.9- 2 .2. Reverse-Transcription Polymerase Chain Reaction (RT- PCR) Analysis. For analysis of the mRNA expression of the target genes, RNA was extracted from SW1353 cells using a commercial RNA MiniPrep Purification Kit (Qiagen) in accordance with the procedures in the manufacturer’s manual. Briefly, cDNA was synthesized using 1 μg of isolated RNA with an RT-PCR One-Step Kit (Bio-Rad, U.S.A.). The SYBR Green-based real-time PCR method was used to measure the mRNA transcripts of the target genes on the ABI 7500 Real-Time PCR platform. The expression levels of each target gene were normalized to GAPDH and calculated using the Figure 1. GPR4 is expressed in human SW1353 chondrocytes. The expression of GPR4 was detected with human umbilical vein endothelial cells (HUVECs) as a positive control. (A) mRNA of GPR4 was measured by reverse-transcription PCR; (B) protein of GPR4 was measured by Western blot analysis. − ΔΔCT 2 method. B https://dx.doi.org/10.1021/acs.chemrestox.0c00111 Chem. Res. Toxicol. XXXX, XXX, XXX−XXX   Chemical Research in Toxicology pubs.acs.org/crt Article Figure 2. AGEs increased the expression of GPR4 in human SW1353 chondrocytes. Cells were stimulated with 50, 100, and 200 μg/mL AGEs for 2 4 h. (A) mRNA of GPR4; (B) protein of GPR4 (**, ****, P < 0.01, 0.0001 vs vehicle group). fold at the protein level (Figure 2B), respectively. Thus, the expression of GPR4 is considerably increased upon exposure to AGEs. antagonism of GPR4 dose-dependently ameliorated this effect to only 2-fold. 3.4. Antagonism of GPR4 and the Inhibition of the Degradation of Type II Collagen. Next, we determined the effect of GPR4 antagonism on the degradation of type II collagen mediated by MMP-3 and MMP-13. The expression of these two enzymes was measured at the mRNA and protein levels using real-time PCR and ELISA. Exposure to AGEs increased the mRNA expression of MMP-3 and MMP-13 to 3.6- and 4.2-fold. However, the addition of 0.5 and 1 μM NE 3 .2. Antagonism of GPR4 and the Reduction of the Expression of Proinflammatory Cytokines Induced by AGEs. Next, we investigated the effects of antagonism of GPR4 using NE 52-QQ57 on the expression of several key inflammatory cytokines by SW1353 chondrocytes treated with AGEs. The molecular structure of NE 52-QQ57 is shown in Figure 3. We measured the mRNA expression of TNF-α, IL- 5 2 2-QQ57 dose-dependently reduced this increase to less than -fold (Figure 7A,B). At the protein level, antagonism of GPR4 dose-dependently reduced the protein secretion of MMP-3 and MMP-13 to only roughly 1.5-fold (Figure 7C,D). To determine whether this decrease in degradative enzymes inhibited the degradation of type II collagen, we employed Western blot analysis. The results in Figure 8 show that stimulation with AGEs induced a decrease in type II collagen of 53%, while antagonism of GPR4 dose-dependently mitigated this decrease to only 28% and 7%, thereby suggesting a potent ability of GPR4 antagonism to prevent MMP- mediated cartilage destruction. Figure 3. Molecular structure of NE 52-QQ57. 1 β, and IL-6 via real-time PCR and found that 0.5 and 1 μM NE 52-QQ57 dose-dependently reduced the AGE-induced increase in TNF-α from 4.5-fold to only 3.2- and 2.1-fold, IL- 3 .5. Antagonism of GPR4 and the Inhibition of the 1β from 3.6-fold to 2.4- and 1.6-fold, and IL-6 from 5.5-fold to 3 .6- and 2.3-fold, respectively (Figures 4A−C). At the protein Activation of NF-κB. NF-κB is widely regarded as a master regulator of inflammation. Here, we determined whether antagonism of GPR4 could suppress the activation of NF-κB. As shown in Figure 9A, there was an increase of 3.5-fold in the nuclear translocation of p65 protein, which was reduced to 2.4- and 1.7-fold by NE 52-QQ57 (Figure 9A). The results of luciferase reporter assay demonstrate that the increase in the luciferase activity of NF-κB of 3-fold induced by AGEs was only 2- and 1.2-fold in the presence of the two respective doses of GPR4 antagonist (Figure 9B). level, a similar effect of GPR4 antagonism was observed, dose- dependently reducing the increased secretion of these three cytokines (Figure 4D−F). 3 .3. Antagonism of GPR4 and the Reduction of the Expression of Inflammatory Mediators Induced by AGEs. Here, we assessed the effect of GPR4 antagonism on the AGE-induced expression of several important inflammatory mediators. First, we determined the effect on iNOS and NO production via real-time PCR, Western blot analysis, and DAF- FM DA staining. As shown in Figure 5A,B, AGEs increased the mRNA and protein expression of iNOS 3.7- and 2.9-fold, while the two doses of GPR4 antagonist dose-dependently reduced these increases to only 2.4- and 1.7-fold at the mRNA level and 4 . DISCUSSION In the present study, we examined the role of the pH-sensing transmembrane receptor GPR4 in human chondrocytes stimulated with AGEs. Researchers have postulated a connection between acidity and osteoarthritis since as far back as 1935,20 and “matrix acidosis” has been cited as a contributor to chondrocyte apoptosis.21 More recent studies have shown, that while many degradative enzymes operate at relatively neutral pH, others cleave type II collagen more efficiently at a lower pH. For example, MMP-3 is most active at a pH of 5.5, while cathepsin K, an acidic cystine endoproteinase, is activated by acidic conditions and operates at a pH of 4.5−6.22 As a newly discovered GPCR, there is 2 .1- and 1.6-fold at the protein level. Consistently, we found that GPR4 antagonism dose-dependently reduced the increase in NO production from 2.9-fold to only 2.2- and 1.7-fold (Figure 5C). Next, we determined the effect on AGE-induced COX2 and PGE2 expression. The mRNA and protein expression of COX2 increased 3.3- and 2.8-fold, while the two doses of GPR4 antagonist reduced these levels to 2.3- and 1 .6-fold at the mRNA level and 2.2- and 1.5-fold at the protein level (Figure 6A,B). The results of ELISA in Figure 6C show that AGEs increased the secretion of PGE2 nearly 4-fold, while C https://dx.doi.org/10.1021/acs.chemrestox.0c00111 Chem. Res. Toxicol. XXXX, XXX, XXX−XXX   Chemical Research in Toxicology pubs.acs.org/crt Article Figure 4. Treatment with the GPR4 antagonist NE 52-QQ57 reduced AGE-induced expression and secretion of pro-inflammatory cytokines TNF- α, IL-1β, and IL-6 in human SW1353 chondrocytes. Cells were stimulated with 100 μg/mL AGEs in the presence or absence of NE 52-QQ57 (0.5 and 1 μM) for 24 h. (A) mRNA of TNF-α; (B) mRNA of IL-1β; (C) mRNA of IL-6; (D) secretions of TNF-α; (E) secretions of IL-1β; (F) secretions of IL-6 (****, P < 0.0001 vs vehicle group; #, ##, ###, ####, P < 0.05, 0.01, 0.001, 0.0001 vs AGEs treatment group). Figure 5. Treatment with the GPR4 antagonist NE 52-QQ57 reducedAGE-induced expression of inducible nitric oxide synthase (iNOS) and production of nitric oxide (NO). Cells were stimulated with 100 μg/mL AGEs in the presence or absence of NE 52-QQ57 (0.5 and 1 μM) for 24 h. (A) mRNA of iNOS as measured by real-time PCR; (B) protein of iNOS as measured by Western blot; (C) production of NO as measured by DAF-FM DA staining (****, P < 0.0001 vs vehicle group; #, ##, ###, ####, P < 0.05, 0.01, 0.001, 0.0001 vs AGEs treatment group). D https://dx.doi.org/10.1021/acs.chemrestox.0c00111 Chem. Res. Toxicol. XXXX, XXX, XXX−XXX   Chemical Research in Toxicology pubs.acs.org/crt Article Figure 6. Treatment with the GPR4 antagonist NE 52-QQ57 prevented AGE-induced expression of cyclooxygenase 2 (COX2) and production of prostaglandin E (PGE ). Cells were stimulated with 100 μg/mL AGEs in the presence or absence of NE 52-QQ57 (0.5, 1 μM) for 24 h. (A) 2 2 mRNA of COX2 as measured by real-time PCR; (B) protein of COX2 as measured by Western blot; (C) production of PGE2 as measured by ELISA (****, P < 0.0001 vs vehicle group; #, ###, ####, P < 0.05, 0.001, 0.0001 vs AGEs treatment group). Figure 7. Treatment with the GPR4 antagonist NE 52-QQ57 inhibited AGE-induced expression of MMP-3 and MMP-13. Cells were stimulated with 100 μg/mL AGEs in the presence or absence of NE 52-QQ57 (0.5 and 1 μM) for 24 h. (A) mRNA of MMP-3; (B) mRNA of MMP-13; (C) protein of MMP-3 as measured by ELISA; (D) protein of MMP-13 as measured by ELISA (****, P < 0.0001 vs vehicle group; ###, ####, P < 0 .001, 0.0001 vs AGEs treatment group). Figure 8. Treatment with the GPR4 antagonist NE 52-QQ57 prevented AGE-induced degradation of type II collagen. Cells were stimulated with 00 μg/mL AGEs in the presence or absence of NE 52-QQ57 (0.5 and 1 μM) for 24 h. Protein level of type II collagen was measured by Western blot analysis (****, P < 0.0001 vs vehicle group; ##, ####, P < 0.01, 0.0001 vs AGEs treatment group). 1 limited research regarding the physiological effects of GPR4. GPR4 acts by altering adenylate cyclase activity and has been shown to be moderately expressed in bone.23 Interestingly, GPR4 has been shown to be expressed in rheumatoid arthritis- E https://dx.doi.org/10.1021/acs.chemrestox.0c00111 Chem. Res. Toxicol. XXXX, XXX, XXX−XXX   Chemical Research in Toxicology pubs.acs.org/crt Article Figure 9. Treatment with the GPR4 antagonist NE 52-QQ57 prevented AGE-induced activation of NF-κB. Cells were stimulated with 100 μg/mL AGEs in the presence or absence of NE 52-QQ57 (0.5 and 1 μM) for 2 h. (A) Nuclear translocation of NF-κB p65; (B) luciferase activity of NF-κB
(****, P < 0.0001 vs vehicle group; ##, ####, P < 0.01, 0.0001 vs AGEs treatment group). affected synoviocytes and synovial tissues, and the associated acidic environment increases the expression of degradative enzymes, including MMPs.24 However, there is little information regarding GPR4 expression in cartilage tissue. Here, we confirmed that GPR4 is expressed in human chondrocytes at both the mRNA and protein levels and AGEs increased the expression of this receptor. However, the possible connection between AGEs and acidity is not yet tered in the cytoplasm in its inactive form. Upon activation, p65 protein, the precursor to NF-κB, is translocated to the nucleus where it triggers the transcription of NF- B and a wide-reaching inflammatory cascade.35 To better elucidate the mechanism behind GPR4 antagonist-mediated improved levels of type II collagen and inflammatory cytokines, we measured the effect on the activation of NF-κB. Indeed, antagonism of GPR4 significantly reduced the level of nuclear p65 and the activity of NF-κB. Taken together, our findings indicate a potential role for the proton-sensing receptor GPR4 in mediating the effects of AGEs in OA. As a newly discovered receptor, little is known about the extent of the effects of GPR4. Further research will provide valuable information regarding the possibilities of GPR4 agonism/antagonism as a potential treatment for a wide range of diseases. The promising results of the present study provide a basis for further research on the type II collagen-rescuing properties of GPR4 antagonism. κ 2 5 clear. Reducing the expression of pro-inflammatory cytokines and other mediators is an important aspect of treatment for countless diseases, including OA. In recent years, OA has come to be recognized as a chronic inflammatory disease, with TNF- α, IL-1β, and IL-6 being of great significance to the pathogenesis of the disease.26 IL-1β induces an inflammatory cascade by triggering the expression of TNF-α, NO, COX2, 2 7 and PGE . Previous research has shown that acidosis 2 increases the expression of TNF-α, PGE , and RNA for bone cell receptor activator of NF-κB ligand (RANKL), a precursor 2 ■ AUTHOR INFORMATION to NF-κB activation.28 It has also been shown that TNF-α and IL-1β promote acidosis-induced chondrocyte apoptosis and reduced type II collagen synthesis.29 Here, we found that, while AGEs increased the expression of these cytokines, antagonism of GPR4 suppressed this effect. GPR4 antagonism also decreased the expression of iNOS, which likely mediated the reduction in NO production. Corresponding Author Bing Chen − Department of Anesthesiology, China-Japan Union Hospital of Jilin University, Changchun City, Jilin Province 130033, China; orcid.org/0000-0002-9638-0161; Phone: +86-431-8499513; Email: [email protected] Authors The progressive degradation of type II collagen is the main hallmark of OA. Type II collagen is the most abundant structural component in articular cartilage and the concen- tration of type II collagen degradative byproducts in urine correlates with the severity of the disease.30 Due to its extremely slow rate of turnover, type II collagen is considered to be essentially irreplaceable.31 Thus, it is of utmost importance to slow or halt the deterioration of type II collagen in patients with OA. MMP-3 (stromelysin-1) and MMP-13 (collagenase-3) are the primary zinc-dependent catabolic Haochuan Liu − Department of Orthopaedics, China-Japan Union Hospital of Jilin University, Changchun City, Jilin Province 130033, China Yulong Liu − Department of Orthopaedics, China-Japan Union Hospital of Jilin University, Changchun City, Jilin Province 130033, China Complete contact information is available at: https://pubs.acs.org/10.1021/acs.chemrestox.0c00111 Notes The authors declare no competing financial interest. enzymes responsible for type II collagen degradation via cleavage of the collagen triple helix at the P4−P11′ site.3 Reducing the expression of these enzymes is an important aspect of a therapeutic approach to slow the progression of OA. In the present study, we found that antagonism of GPR4 significantly reduced the AGE-induced increase in MMP-3 and MMP-13 expression. We further confirmed that this action resulted in a remarkable amelioration of AGE-induced type II collagen degradation. NF-κB is well-recognized as a promoter of MMP-3 and MMP-13 expression and type II collagen 2,33 ■ ACKNOWLEDGMENTS This study is Supported by Young Scholar Research Grant of Chinese Anesthesiologist Association(21900004). ■ REFERENCES (1) Glyn-Jones, S., Palmer, A. J., Agricola, R., Price, A. J., Vincent, T. L., Weinans, H., and Carr, A. J. (2015) Osteoarthritis. Lancet 386 (9991), 376−87. 3 4 degradation. In healthy conditions, NF-κB remains seques- F https://dx.doi.org/10.1021/acs.chemrestox.0c00111 Chem. Res. Toxicol. XXXX, XXX, XXX−XXX   Chemical Research in Toxicology pubs.acs.org/crt Article (2) Ma, F., Li, G., Yu, Y., Xu, J., and Wu, X. (2019) MiR-33b-3p promotes chondrocyte proliferation and inhibits chondrocyte apoptosis and cartilage ECM degradation by targeting DNMT3A in osteoarthritis. Biochem. Biophys. Res. Commun. 519 (2), 430−7. 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