Percutaneous penetration of typical Organophosphate esters under catalysis by Carboxylesterase: Characteristics, mechanism and prediction model

Although the relationship between organophosphate esters (OPEs) percutaneous penetration and their specific physicochemical properties has been investigated, little information is available regarding the percutaneous penetration of OPEs under the interaction of skin enzymes. Herein, we used an in vi...

Full description

Saved in:
Bibliographic Details
Main Authors: Yan Yang, Yuwan Hou, Yonglong Liao, Zeji Huang, Jiejie Pan, Xin Yang, Haojia Chen, Zenghua Qi
Format: Article
Language:English
Published: Elsevier 2025-04-01
Series:Environment International
Subjects:
Online Access:http://www.sciencedirect.com/science/article/pii/S0160412025001709
Tags: Add Tag
No Tags, Be the first to tag this record!
_version_ 1850155270393561088
author Yan Yang
Yuwan Hou
Yonglong Liao
Zeji Huang
Jiejie Pan
Xin Yang
Haojia Chen
Zenghua Qi
author_facet Yan Yang
Yuwan Hou
Yonglong Liao
Zeji Huang
Jiejie Pan
Xin Yang
Haojia Chen
Zenghua Qi
author_sort Yan Yang
collection DOAJ
description Although the relationship between organophosphate esters (OPEs) percutaneous penetration and their specific physicochemical properties has been investigated, little information is available regarding the percutaneous penetration of OPEs under the interaction of skin enzymes. Herein, we used an in vitro skin model to quantitatively assess the skin permeation of six typical OPEs. The in vitro results demonstrated that 0.34–49.87% of OPEs and 0.80–2.95% of their metabolites (mOPEs) penetrated the skin. Notably, triphenyl phosphate (TPHP) and tri-3-cresyl phosphate (TCRP), which exhibit high lipophilicity and large molecular weights, were more likely to be deposited in the skin tissue, thereby hindering their penetration into the body. However, the concentrations of their metabolites, diphenyl hydrogen phosphate (DPHP) and bis(2-methylphenoxy) phosphinic acid (DCRP), in the receptor fluid were approximately six times higher than those of their parent compounds. After in vivo dermal OPE exposure, all parent OPEs were detected in both the stratum corneum and viable tissue (VT). Proteomic analysis and enzymatic hydrolysis experiments revealed that the percutaneous biotransformation of OPEs in VT is mediated primarily by carboxylesterase (CES). A biomimetic bilayer skin membrane based on the CES level in fresh skin yielded results closer to the real skin absorption data of OPEs than prior models. Thus, a more accurate prediction model was established to assess the percutaneous penetration of OPEs. Our results provide valuable insights into the skin absorption of OPEs and emphasize the role of skin CES in calculating and predicting the percutaneous penetration of OPEs.
format Article
id doaj-art-53f1ec6319ae4a9896e601e49680d4cc
institution OA Journals
issn 0160-4120
language English
publishDate 2025-04-01
publisher Elsevier
record_format Article
series Environment International
spelling doaj-art-53f1ec6319ae4a9896e601e49680d4cc2025-08-20T02:24:58ZengElsevierEnvironment International0160-41202025-04-0119810941910.1016/j.envint.2025.109419Percutaneous penetration of typical Organophosphate esters under catalysis by Carboxylesterase: Characteristics, mechanism and prediction modelYan Yang0Yuwan Hou1Yonglong Liao2Zeji Huang3Jiejie Pan4Xin Yang5Haojia Chen6Zenghua Qi7School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China; Synergy Innovation Institute of Guangdong University of Technology, Shantou 515041, ChinaSchool of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China; Synergy Innovation Institute of Guangdong University of Technology, Shantou 515041, ChinaSchool of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou 510006, China; Synergy Innovation Institute of Guangdong University of Technology, Shantou 515041, ChinaSchool of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou 510006, China; Synergy Innovation Institute of Guangdong University of Technology, Shantou 515041, ChinaSchool of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou 510006, ChinaSchool of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou 510006, China; Synergy Innovation Institute of Guangdong University of Technology, Shantou 515041, ChinaSchool of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China; Synergy Innovation Institute of Guangdong University of Technology, Shantou 515041, ChinaSchool of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou 510006, China; Corresponding author.Although the relationship between organophosphate esters (OPEs) percutaneous penetration and their specific physicochemical properties has been investigated, little information is available regarding the percutaneous penetration of OPEs under the interaction of skin enzymes. Herein, we used an in vitro skin model to quantitatively assess the skin permeation of six typical OPEs. The in vitro results demonstrated that 0.34–49.87% of OPEs and 0.80–2.95% of their metabolites (mOPEs) penetrated the skin. Notably, triphenyl phosphate (TPHP) and tri-3-cresyl phosphate (TCRP), which exhibit high lipophilicity and large molecular weights, were more likely to be deposited in the skin tissue, thereby hindering their penetration into the body. However, the concentrations of their metabolites, diphenyl hydrogen phosphate (DPHP) and bis(2-methylphenoxy) phosphinic acid (DCRP), in the receptor fluid were approximately six times higher than those of their parent compounds. After in vivo dermal OPE exposure, all parent OPEs were detected in both the stratum corneum and viable tissue (VT). Proteomic analysis and enzymatic hydrolysis experiments revealed that the percutaneous biotransformation of OPEs in VT is mediated primarily by carboxylesterase (CES). A biomimetic bilayer skin membrane based on the CES level in fresh skin yielded results closer to the real skin absorption data of OPEs than prior models. Thus, a more accurate prediction model was established to assess the percutaneous penetration of OPEs. Our results provide valuable insights into the skin absorption of OPEs and emphasize the role of skin CES in calculating and predicting the percutaneous penetration of OPEs.http://www.sciencedirect.com/science/article/pii/S0160412025001709Organophosphate estersPercutaneous penetrationEnzymolysisCarboxylesterasePrediction model
spellingShingle Yan Yang
Yuwan Hou
Yonglong Liao
Zeji Huang
Jiejie Pan
Xin Yang
Haojia Chen
Zenghua Qi
Percutaneous penetration of typical Organophosphate esters under catalysis by Carboxylesterase: Characteristics, mechanism and prediction model
Environment International
Organophosphate esters
Percutaneous penetration
Enzymolysis
Carboxylesterase
Prediction model
title Percutaneous penetration of typical Organophosphate esters under catalysis by Carboxylesterase: Characteristics, mechanism and prediction model
title_full Percutaneous penetration of typical Organophosphate esters under catalysis by Carboxylesterase: Characteristics, mechanism and prediction model
title_fullStr Percutaneous penetration of typical Organophosphate esters under catalysis by Carboxylesterase: Characteristics, mechanism and prediction model
title_full_unstemmed Percutaneous penetration of typical Organophosphate esters under catalysis by Carboxylesterase: Characteristics, mechanism and prediction model
title_short Percutaneous penetration of typical Organophosphate esters under catalysis by Carboxylesterase: Characteristics, mechanism and prediction model
title_sort percutaneous penetration of typical organophosphate esters under catalysis by carboxylesterase characteristics mechanism and prediction model
topic Organophosphate esters
Percutaneous penetration
Enzymolysis
Carboxylesterase
Prediction model
url http://www.sciencedirect.com/science/article/pii/S0160412025001709
work_keys_str_mv AT yanyang percutaneouspenetrationoftypicalorganophosphateestersundercatalysisbycarboxylesterasecharacteristicsmechanismandpredictionmodel
AT yuwanhou percutaneouspenetrationoftypicalorganophosphateestersundercatalysisbycarboxylesterasecharacteristicsmechanismandpredictionmodel
AT yonglongliao percutaneouspenetrationoftypicalorganophosphateestersundercatalysisbycarboxylesterasecharacteristicsmechanismandpredictionmodel
AT zejihuang percutaneouspenetrationoftypicalorganophosphateestersundercatalysisbycarboxylesterasecharacteristicsmechanismandpredictionmodel
AT jiejiepan percutaneouspenetrationoftypicalorganophosphateestersundercatalysisbycarboxylesterasecharacteristicsmechanismandpredictionmodel
AT xinyang percutaneouspenetrationoftypicalorganophosphateestersundercatalysisbycarboxylesterasecharacteristicsmechanismandpredictionmodel
AT haojiachen percutaneouspenetrationoftypicalorganophosphateestersundercatalysisbycarboxylesterasecharacteristicsmechanismandpredictionmodel
AT zenghuaqi percutaneouspenetrationoftypicalorganophosphateestersundercatalysisbycarboxylesterasecharacteristicsmechanismandpredictionmodel