Lipid peroxidation-derived aldehydes,such as acrolein,the most reactive aldehyde,have emerged as key culprits in sustaining post-spinal cord injury(SCI)secondary pathologies leading to functional loss.Strong evidence ...Lipid peroxidation-derived aldehydes,such as acrolein,the most reactive aldehyde,have emerged as key culprits in sustaining post-spinal cord injury(SCI)secondary pathologies leading to functional loss.Strong evidence suggests that mitochondrial aldehyde dehydrogenase-2(ALDH2),a key oxidoreductase and powerful endogenous anti-aldehyde machinery,is likely important for protecting neurons from aldehydesmediated degeneration.Using a rat model of spinal cord contusion injury and recently discovered ALDH2 activator(Alda-1),we planned to validate the aldehyde-clearing and neuroprotective role of ALDH2.Over an acute 2 day period post injury,we found that ALDH2 expression was significantly lowered post-SCI,but not so in rats given Alda-1.This lower enzymatic expression may be linked to heightened acrolein-ALDH2 adduction,which was revealed in co-immunoprecipitation experiments.We have also found that administration of Alda-1 to SCI rats significantly lowered acrolein in the spinal cord,and reduced cyst pathology.In addition,Alda-1 treatment also resulted in significant improvement of motor function and attenuated post-SCI mechanical hypersensitivity up to 28 days post-SCI.Finally,ALDH2 was found to play a critical role in in vitro protection of PC12 cells from acrolein exposure.It is expected that the outcome of this study will broaden and enhance anti-aldehyde strategies in combating post-SCI neurodegeneration and potentially bring treatment to millions of SCI victims.All animal work was approved by Purdue Animal Care and Use Committee(approval No.1111000095)on January 1,2021.展开更多
Despite of its great importance, the detailed molecular mechanism for carbohydrate pyrolysis remains poorly understood. We perform a density functional study with a newly developed XYG3 functional on the processes for...Despite of its great importance, the detailed molecular mechanism for carbohydrate pyrolysis remains poorly understood. We perform a density functional study with a newly developed XYG3 functional on the processes for D-glucose pyrolysis to acrolein. The most feasible reaction pathway starts from an isomerization from D-glucose to D-fructose, which then undergoes a cyclic Grob fragmentation, followed by a concerted electrocyclic dehydration to yield acrolein. This mechanism can account for the known experimental results.展开更多
Clinical advances in the treatment of intracranial hemorrhage(ICH)are restricted by the incomplete understanding of the molecular mechanisms contributing to secondary brain injury.Acrolein is a highly active unsaturat...Clinical advances in the treatment of intracranial hemorrhage(ICH)are restricted by the incomplete understanding of the molecular mechanisms contributing to secondary brain injury.Acrolein is a highly active unsaturated aldehyde which has been implicated in many nervous system diseases.Our results indicated a significant increase in the level of acrolein after ICH in mouse brain.In primary neurons,acrolein induced an increase in mitochondrial fragmentation,loss of mitochondrial membrane potential,generation of reactive oxidative species,and release of mitochondrial cytochrome c.Mechanistically,acrolein facilitated the translocation of dynaminrelated protein 1(Drpl)from the cytoplasm onto the mitochondrial membrane and led to excessive mitochondrial fission.Further studies found that treatment with hydralazine(an acrolein scavenger)significantly reversed Drpl translocation and the morphological damage of mitochondria after ICH.In parallel,the neural apoptosis,brain edema,and neurological functional deficits induced by ICH were also remarkably alleviated.In conclusion,our results identify acrolein as an important contributor to the secondary brain injury following ICH.Meanwhile,we uncovered a novel mechanism by which Drpl-mediated mitochondrial oxidative damage is involved in acroleininduced brain injury.展开更多
Acrolein,known as one of the most common reactive carbonyl species,is a toxic small molecule affecting human health in daily life.This study is focused on the scavenging abilities and mechanism of ferulic acid and som...Acrolein,known as one of the most common reactive carbonyl species,is a toxic small molecule affecting human health in daily life.This study is focused on the scavenging abilities and mechanism of ferulic acid and some other phenolic acids against acrolein.Among the 13 phenolic compounds investigated,ferulic acid was found to have the highest efficiency in scavenging acrolein under physiological 8nditions.Ferulic acid remained at(3.04±1.89)%and acrolein remained at(29.51±4.44)%after being incubated with each other for 24 h.The molecular mechanism of the detoxifying process was also studied.Detoxifying products,namely 2-methoxy-4-vinyIphenol(product 21)and 5-(4-hydroxy-3-methoxyphenyl)pent-4-enal(product 22),were identified though nuclear magnetic resonanee(NMR)and gas chromatography-mass spectrometry(GC-MS),after the scavenging process.Ferulic acid showed significant activity in scavenging acrolein under physiological conditions.This study indicates a new method for inhibiting damage from acrolein.展开更多
A mesoporous sulfated zirconia-silica catalyst bearing only Br？nsted acid sites converted glycerol to acrolein in 81%yield with 82% selectivity.Space time yield as high as 9.0 mmol h^（-1） g_（cat）^（-1） was achie...A mesoporous sulfated zirconia-silica catalyst bearing only Br？nsted acid sites converted glycerol to acrolein in 81%yield with 82% selectivity.Space time yield as high as 9.0 mmol h^（-1） g_（cat）^（-1） was achieved even at a low reaction temperature of 523 K.The catalytic activity and selectivity were higher than those of typical sulfated zirconia.It is proposed that the milder acidity due to dilution of zirconium species by silica and large pore size for faster diffusion contributed towards the better catalytic performance.展开更多
Traumatic brain injury(TBI)-induced coagulopathy has increasingly been recognized as a significant risk factor for poor outcomes,but the pathogenesis remains poorly understood.In this study,we aimed to investigate the...Traumatic brain injury(TBI)-induced coagulopathy has increasingly been recognized as a significant risk factor for poor outcomes,but the pathogenesis remains poorly understood.In this study,we aimed to investigate the causal role of acrolein,a typical lipid peroxidation product,in TBI-induced coagulopathy,and further explore the underlying molecular mechanisms.We found that the level of plasma acrolein in TBI patients suffering from coagulopathy was higher than that in those without coagulopathy.Using a controlled cortical impact mouse model,we demonstrated that the acrolein scavenger phenelzine prevented TBI-induced coagulopathy and recombinant ADAMTS-13 prevented acrolein-induced coagulopathy by cleaving von Willebrand factor(VWF).Our results showed that acrolein may contribute to an early hypercoagulable state after TBI by regulating VWF secretion.mRNA sequencing(mRNA-seq)and transcriptome analysis indicated that acrolein over-activated autophagy,and subsequent experiments revealed that acrolein activated autophagy partly by regulating the Akt/mTOR pathway.In addition,we demonstrated that acrolein was produced in the perilesional cortex,affected endothelial cell integrity,and disrupted the blood-brain barrier.In conclusion,in this study we uncovered a novel pro-coagulant effect of acrolein that may contribute to TBI-induced coagulopathy and vascular leakage,providing an alternative therapeutic target.展开更多
Precursor decomposition was used for the preparation of VTeO/SBA-15 catalyst for the selective oxidation of propane to acrolein. The catalyst shows a better performance compared with those prepared by conventional imp...Precursor decomposition was used for the preparation of VTeO/SBA-15 catalyst for the selective oxidation of propane to acrolein. The catalyst shows a better performance compared with those prepared by conventional impregnant method. A yield of 9.3% of acrolein was achieved with 2% V loadings at 500 ℃. XRD, N2-adsorption, H2-TPR, Py-IR and XPS measurements were used to unclose the relationship between the structure and performance of the catalyst.展开更多
Glycerol dehydration to acrolein over a series of supported silicotungstic acid catalysts(SiWx‐Al/Zry)was investigated.Characterization results showed that the final catalyst had high thermal stability,a large pore d...Glycerol dehydration to acrolein over a series of supported silicotungstic acid catalysts(SiWx‐Al/Zry)was investigated.Characterization results showed that the final catalyst had high thermal stability,a large pore diameter,strong Lewis acidic sites,and a large specific surface area.X‐ray photoelectron survey spectra clearly showed peaks attributable to W(W4f=35.8eV),Al2O3(Al2p=74.9eV),and ZrO2(Zr3d=182.8eV).The highest acrolein selectivity achieved was87.3%at97%glycerol conversion over the SiW20‐Al/Zr10catalyst.The prepared catalysts were highly active and selective for acrolein formation even after40h because of the presence of high concentrations of Lewis acidic sites,which significantly reduced the amount of coke on the catalyst surface.Response surface methodology optimization showed that87.7%acrolein selectivity at97.0%glycerol conversion could be obtained under the following optimal reaction conditions:0.5wt%catalyst,reaction temperature300°C,and feed glycerol concentration10wt%.Evaluation of a mass‐transfer‐limited regime showed the absence of internal and external diffusions over pellets of diameter dP<20μm.These results show that glycerol dehydration over a strong Lewis acid catalyst is a promising method for acrolein production.展开更多
In the hours to weeks following traumatic spinal cord injuries （SCI）, biochemical processes are initiated that further damage the tissue within and surrounding the initial injury site： a process termed secondary in...In the hours to weeks following traumatic spinal cord injuries （SCI）, biochemical processes are initiated that further damage the tissue within and surrounding the initial injury site： a process termed secondary injury. Acrolein, a highly reactive unsaturated aldehyde, has been shown to play a major role in the secondary injury by contributing significantly to both motor and sensory defi- cits. In particular, efforts have been made to eluddate the mechanisms of acrolein-mediated dam- age at the cellular level and the resulting paralysis and neuropathic pain. In this review, we will highlight the recent developments in the understanding of the mechanisms of acrolein in motor and sensory dysfunction in animal models of SCI. We will also discuss the therapeutic benefits of using acrolein scavengers to attenuate acrolein-mediated neuronal damage following SCI.展开更多
Oxide-supported copper-containing materials have attracted considerable research attention as promising candidates for acrolein formation.Nevertheless,the elucidation of the structure-performance relationships for the...Oxide-supported copper-containing materials have attracted considerable research attention as promising candidates for acrolein formation.Nevertheless,the elucidation of the structure-performance relationships for these systems remains a scientific challenge.In this work,copper oxide clusters deposited on a high-surface-area silica support were synthesized via a deposition-precipitation approach and exhibited remarkable catalytic reactivity(up to 25.5%conversion and 66.8%selectivity)in the propylene-selective oxidation of acrolein at 300℃.Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy combined with X-ray absorption fine structure measurements of the catalyst before and after the reaction confirmed the transformation of the small-sized copper oxide(CuO)clusters into cuprous oxide(Cu2O)clusters.With the aid of in situ X-ray diffraction and in situ dual beam Fourier transform infrared spectroscopy(DB-FTIR),the allyl intermediate(CH2=CHCH2*)was clearly observed,along with the as-formed Cu2O species.The intermediate can react with oxygen atoms from neighboring Cu2O species to form acrolein during the catalytic process,and the small-sized Cu2O clusters play a crucial role in the generation of acrolein via the selective oxidation of propylene.展开更多
Direct epoxidation of propylene with H_(2)/O_(2),being the dream reaction for propylene oxide(PO)production,has raised wide scientific and industrial interests.Fundamentally understanding the formation mechanism of ac...Direct epoxidation of propylene with H_(2)/O_(2),being the dream reaction for propylene oxide(PO)production,has raised wide scientific and industrial interests.Fundamentally understanding the formation mechanism of acrolein,as the main by-product of this epoxidation process,is very important to achieve the high yield of PO.In this study,we perform the spin-polarized density functional theory(DFT)calculations to investigate the reaction pathway from propylene to acrolein over two representative Au surfaces,that is,Au(111)and Au(100),which incorporates propylene adsorption,methyl hydrogen activation and acrolein formation.The results show that the oxygenated species(mainly O^(*),OH^(*)and OOH^(*))are able to stabilize the adsorption of propylene to decrease the energy barrier for its activation.It is demonstrated that the OOH^(*)on Au(111)surface emerges as the most easily formed oxygenated species via the H-assisted O_(2) dissociation,which is also the most active for the cleavage of methyl CAH bond in propylene.Furthermore,three pathways of acrolein formation activated by O^(*)/OH^(*)/OOH^(*)are analyzed,in which O^(*)is found as the key species to form acrolein.Finally,Bader charge analysis was conducted to explore the reasons behind the promotion effect of the oxygenated species.The insights reported here could be valuable in the design and optimization of gold catalysts for the direct epoxidation of propylene.展开更多
Several Mo-V-Te-O mixed metal oxides catalysts with different dopant were prepared and used for catalytic oxidation propane to acrolein. It was revealed that the addition of P could greatly improve the performance of ...Several Mo-V-Te-O mixed metal oxides catalysts with different dopant were prepared and used for catalytic oxidation propane to acrolein. It was revealed that the addition of P could greatly improve the performance of the Mo-V-Te-O catalyst. The catalysts were examined by XRD and H2-TPR. The XRD characteristic of the Mo-V-Te-P-O showed that the addition of P could aggrandize the (V0.07Mo0.93)5O14 phase. H2-TPR illuminated that the MoV0.3Te0.23P0.15On catalyst took on the best redox ability.展开更多
The increase of biodiesel production results in the accumulation of glycerol, which requires an increasing demand towards the study of chemical application of glycerol. Glycerol has to be transformed to other valuable...The increase of biodiesel production results in the accumulation of glycerol, which requires an increasing demand towards the study of chemical application of glycerol. Glycerol has to be transformed to other valuable chemicals, which can be used as starting materials for organic synthesis. With the final goal to find a reasonable solution for this problem we have studied the dehydration of glycerol in liquid phase using a supported HPA catalyst and developed an environmentally benign production of acrolein. Our method does not have any extreme conditions and produces a total conversion with high (93%) selectivity.展开更多
A series of MoTe_（0.15）V_（0.1）P_xO_n catalysts supported on the SiC were prepared by incipient wetness impregnation.The addition of P to MoTe_（0.15）V_（0.1）O_n/SiC catalysts improved the catalytic performance o...A series of MoTe_（0.15）V_（0.1）P_xO_n catalysts supported on the SiC were prepared by incipient wetness impregnation.The addition of P to MoTe_（0.15）V_（0.1）O_n/SiC catalysts improved the catalytic performance of selective oxidation from propane to acrolein（ACR）,and the catalyst showed highest selectivity（33.7%） and yield（10.7%） when x = 0.05.The MoTe_（0.15）V_（0.1）P_xO_n/SiC catalysts have been characterized by XRD,H_2-TPR,Raman,XPS and NH_3-TPD.The results indicated that a little H_3PMo_（12）O_（40） heteropoly acid and（VO）_2P_2O_7 formed and MoO_3 phase lessened after addition of P.The addition of P promoted the active species dispersed,increased the acidity on the surface,as well as might make the redox process easier.These significant differences improved the activity and selectivity of ACR.展开更多
The gas-phase dehydration of glycerol was conducted over HPW/MCM-41 catalysts,which were prepared by impregnation of different amount of H3PW（12）O（40）（HPW）on the MCM-41 support.The samples were characterized by ...The gas-phase dehydration of glycerol was conducted over HPW/MCM-41 catalysts,which were prepared by impregnation of different amount of H3PW（12）O（40）（HPW）on the MCM-41 support.The samples were characterized by XRD,N2 physisorption,FTIR,NH3-TPD,and pyridine-FTIR measurements.N2 physisorption results suggested that the uniform framework of MCM-41 could still be well maintained after modified with HPW.Pyridine-FTIR experiments indicate that HPW modified MCM-41 can generate rich Br？nsted acid sites.Moreover,Brnsted acid sites facilitated to improve acrolein selectivity.Under the optimized reaction conditions：40wt%HPW loading,20%glycerol concentration,and 320℃reaction temperature,the glycerol conversion and acrolein selectivity reach 85%and 80%,respectively.展开更多
Photodecarbonylation reaction of acrolein at 193nm was investigated by ab initio molecular orbital method.Our result supports photodecarbonylation mechanisms proposed by Fujimoto,and predicts that the reaction should ...Photodecarbonylation reaction of acrolein at 193nm was investigated by ab initio molecular orbital method.Our result supports photodecarbonylation mechanisms proposed by Fujimoto,and predicts that the reaction should occur in ~3ππ potential energy surface prior to the ~1ππ potential energy surface.展开更多
The circadian clock is crucial for the progression of cardiovascular diseases.Our previous studies showed that acrolein,an environmental pollutant,exacerbated atherosclerosis by reducing CLOCK/BMAL1 levels and disrupt...The circadian clock is crucial for the progression of cardiovascular diseases.Our previous studies showed that acrolein,an environmental pollutant,exacerbated atherosclerosis by reducing CLOCK/BMAL1 levels and disrupting circadian rhythm;in contrast,intermittent fasting(IF),a dietary regimen,ameliorated acrolein-induced atherosclerosis.In the current study,mice were administered acrolein at a dose of 3 mg/(kg·day)via drinking water and subjected to IF for 18 h(from 0:00 to 18:00).We observed that IF reduced the formation of aortic lesions accelerated by acrolein in Apo E-/-mice.Upon exposure to acrolein,the expression of Rel A,Il1b,and Tnf increased in the liver and heart tissues,but these changes were reversed by IF treatment.Notably,IF treatment upregulated the expression of adenosine monophosphate(AMP)-activated protein kinase catalytic subunit alpha-1(AMPKα1),p-AMPKα1,and sirtuin 1(SIRT1),while inhibiting acrolein-induced mitogen-activated protein kinase(MAPK)activation.Additionally,the expression of circadian genes Clock/Bmal1 was suppressed and disrupted by acrolein,whereas IF restored their expression.Moreover,consistent with the in vivo findings,shortterm starvation in vitro,as a fasting cell model,alleviated the dysregulation of CLOCK/BMAL1 and upregulated SIRT1 expression by modulating the AMPK and reactive oxygen species(ROS)-MAPK pathways activated by acrolein.In summary,we demonstrated that IF suppressed the ROS-MAPK pathway but activated the AMPK pathway to enhance the expression of circadian clock genes,thereby ameliorating acrolein-induced atherogenesis,which may shed light on strategies for preventing cardiovascular diseases.展开更多
We report the first example of catalytic asymmetric Morita-Baylis-Hillman reaction of acrolein with aromatic aldehydes. The use of 10 mol% of Hatakeyama＇s catalyst β-isocupreidine C4, in combination with 20 mol% of ...We report the first example of catalytic asymmetric Morita-Baylis-Hillman reaction of acrolein with aromatic aldehydes. The use of 10 mol% of Hatakeyama＇s catalyst β-isocupreidine C4, in combination with 20 mol% of 2,6-dimethoxybenzoic acid, could catalyze the reaction to give the desired products in up to 81% ee.展开更多
Background:The mechanisms underlying lesions of dopaminergic(DA)neurons,an essential pathology of Parkinson’s disease(PD),are largely unknown,although oxidative stress is recognized as a key factor.We have previously...Background:The mechanisms underlying lesions of dopaminergic(DA)neurons,an essential pathology of Parkinson’s disease(PD),are largely unknown,although oxidative stress is recognized as a key factor.We have previously shown that the pro-oxidative aldehyde acrolein is a critical factor in PD pathology,and that acrolein scavenger hydralazine can reduce the elevated acrolein,mitigate DA neuron death,and alleviate motor deficits in a 6-hydroxydopamine(6-OHDA)rat model.As such,we hypothesize that a structurally distinct acrolein scavenger,dimercaprol(DP),can also offer neuroprotection and behavioral benefits.Methods:DP was used to lower the elevated levels of acrolein in the basal ganglia of 6-OHDA rats.The acrolein levels and related pathologies were measured by immunohistochemistry.Locomotor and behavioral effects of 6-OHDA injections and DP treatment were examined using the open field test and rotarod test.Pain was assessed using mechanical allodynia,cold hypersensitivity,and plantar tests.Finally,the effects of DP were assessed in vitro on SK-N-SH dopaminergic cells exposed to acrolein.Results:DP reduced acrolein and reversed the upregulation of pain-sensing transient receptor potential ankyrin 1(TRPA1)channels in the substantia nigra,striatum,and cortex.DP also mitigated both motor and sensory deficits typical of PD.In addition,DP lowered acrolein and protected DA-like cells in vitro.Acrolein’s ability to upregulate TRPA1 was also verified in vitro using cell lines.Conclusions:These results further elucidated the acrolein-mediated pathogenesis and reinforced the critical role of acrolein in PD while providing strong arguments for anti-acrolein treatments as a novel and feasible strategy to combat neurodegeneration in PD.Considering the extensive involvement of acrolein in various nervous system illnesses and beyond,anti-acrolein strategies may have wide applications and broad impacts on human health.展开更多
Propylene epoxidation by H_(2)and O_(2)to propylene oxide(PO)over the Au-Ti bifunctional catalysts,as an ideal reaction for PO production,has attracted great interest.Revealing the mechanism of acrolein formation is o...Propylene epoxidation by H_(2)and O_(2)to propylene oxide(PO)over the Au-Ti bifunctional catalysts,as an ideal reaction for PO production,has attracted great interest.Revealing the mechanism of acrolein formation is of great importance for understanding the mechanism of molecular oxygen activation and the formation of hydroperoxo species on the Au sites.Here,we investigate the reaction mechanism of propylene oxidation to acrolein on the Au/uncalcined TS-1(Au/TS-1-B)catalyst through a combination of multiple characterization,H_(2)/D_(2)exchange,kinetics experiment,and modeling.The Ti sites are found to be non-essential to acrolein formation.Moreover,the acrolein formation on the Au/TS-1-B catalyst is confirmed to be promoted by H_(2)through hydroperoxo species formation,which includes two main steps:propylene dehydrogenation to*C_(3)H_(5)with the aid of*OOH species,and*C_(3)H_(5)oxidation by*OOH to acrolein.The latter step is determined to be the rate-determining step because the corresponding kinetics model gives the best description for experimental results.This work not only provides kinetics insights for the propylene hydro-oxidation to acrolein on the Au-Ti bifunctional catalysts,but also facilitates the rational design of Au catalysts with high activity and selectivity in the direct propylene epoxidation with H_(2)and O_(2).展开更多
基金supported by a grant from National Institute of Neurological Disorders and Stroke R21(No.1R21NS115094-01)。
文摘Lipid peroxidation-derived aldehydes,such as acrolein,the most reactive aldehyde,have emerged as key culprits in sustaining post-spinal cord injury(SCI)secondary pathologies leading to functional loss.Strong evidence suggests that mitochondrial aldehyde dehydrogenase-2(ALDH2),a key oxidoreductase and powerful endogenous anti-aldehyde machinery,is likely important for protecting neurons from aldehydesmediated degeneration.Using a rat model of spinal cord contusion injury and recently discovered ALDH2 activator(Alda-1),we planned to validate the aldehyde-clearing and neuroprotective role of ALDH2.Over an acute 2 day period post injury,we found that ALDH2 expression was significantly lowered post-SCI,but not so in rats given Alda-1.This lower enzymatic expression may be linked to heightened acrolein-ALDH2 adduction,which was revealed in co-immunoprecipitation experiments.We have also found that administration of Alda-1 to SCI rats significantly lowered acrolein in the spinal cord,and reduced cyst pathology.In addition,Alda-1 treatment also resulted in significant improvement of motor function and attenuated post-SCI mechanical hypersensitivity up to 28 days post-SCI.Finally,ALDH2 was found to play a critical role in in vitro protection of PC12 cells from acrolein exposure.It is expected that the outcome of this study will broaden and enhance anti-aldehyde strategies in combating post-SCI neurodegeneration and potentially bring treatment to millions of SCI victims.All animal work was approved by Purdue Animal Care and Use Committee(approval No.1111000095)on January 1,2021.
基金Acknowledgments This work was supported by the National Natural Science Foundation of China （No.I0774126） and the Ministry of Science and Technology （No.2007CB815206 and No.2011CB808505）.
文摘Despite of its great importance, the detailed molecular mechanism for carbohydrate pyrolysis remains poorly understood. We perform a density functional study with a newly developed XYG3 functional on the processes for D-glucose pyrolysis to acrolein. The most feasible reaction pathway starts from an isomerization from D-glucose to D-fructose, which then undergoes a cyclic Grob fragmentation, followed by a concerted electrocyclic dehydration to yield acrolein. This mechanism can account for the known experimental results.
基金This work was supported by grants from the National Natural Science Foundation of China(81630027,81571215)and the Chang Jiang Scholar Program of China.
文摘Clinical advances in the treatment of intracranial hemorrhage(ICH)are restricted by the incomplete understanding of the molecular mechanisms contributing to secondary brain injury.Acrolein is a highly active unsaturated aldehyde which has been implicated in many nervous system diseases.Our results indicated a significant increase in the level of acrolein after ICH in mouse brain.In primary neurons,acrolein induced an increase in mitochondrial fragmentation,loss of mitochondrial membrane potential,generation of reactive oxidative species,and release of mitochondrial cytochrome c.Mechanistically,acrolein facilitated the translocation of dynaminrelated protein 1(Drpl)from the cytoplasm onto the mitochondrial membrane and led to excessive mitochondrial fission.Further studies found that treatment with hydralazine(an acrolein scavenger)significantly reversed Drpl translocation and the morphological damage of mitochondria after ICH.In parallel,the neural apoptosis,brain edema,and neurological functional deficits induced by ICH were also remarkably alleviated.In conclusion,our results identify acrolein as an important contributor to the secondary brain injury following ICH.Meanwhile,we uncovered a novel mechanism by which Drpl-mediated mitochondrial oxidative damage is involved in acroleininduced brain injury.
基金Project supported by the National Natural Science Foundation of China(Nos.21327010 and 21372199)
文摘Acrolein,known as one of the most common reactive carbonyl species,is a toxic small molecule affecting human health in daily life.This study is focused on the scavenging abilities and mechanism of ferulic acid and some other phenolic acids against acrolein.Among the 13 phenolic compounds investigated,ferulic acid was found to have the highest efficiency in scavenging acrolein under physiological 8nditions.Ferulic acid remained at(3.04±1.89)%and acrolein remained at(29.51±4.44)%after being incubated with each other for 24 h.The molecular mechanism of the detoxifying process was also studied.Detoxifying products,namely 2-methoxy-4-vinyIphenol(product 21)and 5-(4-hydroxy-3-methoxyphenyl)pent-4-enal(product 22),were identified though nuclear magnetic resonanee(NMR)and gas chromatography-mass spectrometry(GC-MS),after the scavenging process.Ferulic acid showed significant activity in scavenging acrolein under physiological conditions.This study indicates a new method for inhibiting damage from acrolein.
基金supported by Grant-in-Aid for Research Activity Start-up(KAKENHI,21860004)for Young Scientists(KAKENHI,26709060) from Japan Society for the Promotion of Science(JSPS)
文摘A mesoporous sulfated zirconia-silica catalyst bearing only Br？nsted acid sites converted glycerol to acrolein in 81%yield with 82% selectivity.Space time yield as high as 9.0 mmol h^（-1） g_（cat）^（-1） was achieved even at a low reaction temperature of 523 K.The catalytic activity and selectivity were higher than those of typical sulfated zirconia.It is proposed that the milder acidity due to dilution of zirconium species by silica and large pore size for faster diffusion contributed towards the better catalytic performance.
基金the National Natural Science Foundation of China(81630027).
文摘Traumatic brain injury(TBI)-induced coagulopathy has increasingly been recognized as a significant risk factor for poor outcomes,but the pathogenesis remains poorly understood.In this study,we aimed to investigate the causal role of acrolein,a typical lipid peroxidation product,in TBI-induced coagulopathy,and further explore the underlying molecular mechanisms.We found that the level of plasma acrolein in TBI patients suffering from coagulopathy was higher than that in those without coagulopathy.Using a controlled cortical impact mouse model,we demonstrated that the acrolein scavenger phenelzine prevented TBI-induced coagulopathy and recombinant ADAMTS-13 prevented acrolein-induced coagulopathy by cleaving von Willebrand factor(VWF).Our results showed that acrolein may contribute to an early hypercoagulable state after TBI by regulating VWF secretion.mRNA sequencing(mRNA-seq)and transcriptome analysis indicated that acrolein over-activated autophagy,and subsequent experiments revealed that acrolein activated autophagy partly by regulating the Akt/mTOR pathway.In addition,we demonstrated that acrolein was produced in the perilesional cortex,affected endothelial cell integrity,and disrupted the blood-brain barrier.In conclusion,in this study we uncovered a novel pro-coagulant effect of acrolein that may contribute to TBI-induced coagulopathy and vascular leakage,providing an alternative therapeutic target.
基金Supported by the Ministry of Science and Technology of China(No. 2005CB221408)the National Natural Science Founda-tion of China(Nos. 20423002, 20571061)Key Scientific Project of Fujian Province, China(No. 2005HZ01-3)
文摘Precursor decomposition was used for the preparation of VTeO/SBA-15 catalyst for the selective oxidation of propane to acrolein. The catalyst shows a better performance compared with those prepared by conventional impregnant method. A yield of 9.3% of acrolein was achieved with 2% V loadings at 500 ℃. XRD, N2-adsorption, H2-TPR, Py-IR and XPS measurements were used to unclose the relationship between the structure and performance of the catalyst.
基金the Ministry of Science, Technology and Innovation (MOSTI), Malaysia for supporting the project under project no. 03–01–06–SF0963
文摘Glycerol dehydration to acrolein over a series of supported silicotungstic acid catalysts(SiWx‐Al/Zry)was investigated.Characterization results showed that the final catalyst had high thermal stability,a large pore diameter,strong Lewis acidic sites,and a large specific surface area.X‐ray photoelectron survey spectra clearly showed peaks attributable to W(W4f=35.8eV),Al2O3(Al2p=74.9eV),and ZrO2(Zr3d=182.8eV).The highest acrolein selectivity achieved was87.3%at97%glycerol conversion over the SiW20‐Al/Zr10catalyst.The prepared catalysts were highly active and selective for acrolein formation even after40h because of the presence of high concentrations of Lewis acidic sites,which significantly reduced the amount of coke on the catalyst surface.Response surface methodology optimization showed that87.7%acrolein selectivity at97.0%glycerol conversion could be obtained under the following optimal reaction conditions:0.5wt%catalyst,reaction temperature300°C,and feed glycerol concentration10wt%.Evaluation of a mass‐transfer‐limited regime showed the absence of internal and external diffusions over pellets of diameter dP<20μm.These results show that glycerol dehydration over a strong Lewis acid catalyst is a promising method for acrolein production.
文摘In the hours to weeks following traumatic spinal cord injuries （SCI）, biochemical processes are initiated that further damage the tissue within and surrounding the initial injury site： a process termed secondary injury. Acrolein, a highly reactive unsaturated aldehyde, has been shown to play a major role in the secondary injury by contributing significantly to both motor and sensory defi- cits. In particular, efforts have been made to eluddate the mechanisms of acrolein-mediated dam- age at the cellular level and the resulting paralysis and neuropathic pain. In this review, we will highlight the recent developments in the understanding of the mechanisms of acrolein in motor and sensory dysfunction in animal models of SCI. We will also discuss the therapeutic benefits of using acrolein scavengers to attenuate acrolein-mediated neuronal damage following SCI.
文摘Oxide-supported copper-containing materials have attracted considerable research attention as promising candidates for acrolein formation.Nevertheless,the elucidation of the structure-performance relationships for these systems remains a scientific challenge.In this work,copper oxide clusters deposited on a high-surface-area silica support were synthesized via a deposition-precipitation approach and exhibited remarkable catalytic reactivity(up to 25.5%conversion and 66.8%selectivity)in the propylene-selective oxidation of acrolein at 300℃.Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy combined with X-ray absorption fine structure measurements of the catalyst before and after the reaction confirmed the transformation of the small-sized copper oxide(CuO)clusters into cuprous oxide(Cu2O)clusters.With the aid of in situ X-ray diffraction and in situ dual beam Fourier transform infrared spectroscopy(DB-FTIR),the allyl intermediate(CH2=CHCH2*)was clearly observed,along with the as-formed Cu2O species.The intermediate can react with oxygen atoms from neighboring Cu2O species to form acrolein during the catalytic process,and the small-sized Cu2O clusters play a crucial role in the generation of acrolein via the selective oxidation of propylene.
基金financially supported by the Research Fund for National Key Research and Development Program of China (2021YFA1501403)the National Natural Science Foundation of China (22208094,22038003,21922803,22178100)+1 种基金the Innovation Program of Shanghai Municipal Education Commission,the Program of Shanghai Academic/Technology Research Leader (21XD1421000)the Shanghai Science and Technology Innovation Action Plan (22JC1403800)。
文摘Direct epoxidation of propylene with H_(2)/O_(2),being the dream reaction for propylene oxide(PO)production,has raised wide scientific and industrial interests.Fundamentally understanding the formation mechanism of acrolein,as the main by-product of this epoxidation process,is very important to achieve the high yield of PO.In this study,we perform the spin-polarized density functional theory(DFT)calculations to investigate the reaction pathway from propylene to acrolein over two representative Au surfaces,that is,Au(111)and Au(100),which incorporates propylene adsorption,methyl hydrogen activation and acrolein formation.The results show that the oxygenated species(mainly O^(*),OH^(*)and OOH^(*))are able to stabilize the adsorption of propylene to decrease the energy barrier for its activation.It is demonstrated that the OOH^(*)on Au(111)surface emerges as the most easily formed oxygenated species via the H-assisted O_(2) dissociation,which is also the most active for the cleavage of methyl CAH bond in propylene.Furthermore,three pathways of acrolein formation activated by O^(*)/OH^(*)/OOH^(*)are analyzed,in which O^(*)is found as the key species to form acrolein.Finally,Bader charge analysis was conducted to explore the reasons behind the promotion effect of the oxygenated species.The insights reported here could be valuable in the design and optimization of gold catalysts for the direct epoxidation of propylene.
文摘Several Mo-V-Te-O mixed metal oxides catalysts with different dopant were prepared and used for catalytic oxidation propane to acrolein. It was revealed that the addition of P could greatly improve the performance of the Mo-V-Te-O catalyst. The catalysts were examined by XRD and H2-TPR. The XRD characteristic of the Mo-V-Te-P-O showed that the addition of P could aggrandize the (V0.07Mo0.93)5O14 phase. H2-TPR illuminated that the MoV0.3Te0.23P0.15On catalyst took on the best redox ability.
文摘The increase of biodiesel production results in the accumulation of glycerol, which requires an increasing demand towards the study of chemical application of glycerol. Glycerol has to be transformed to other valuable chemicals, which can be used as starting materials for organic synthesis. With the final goal to find a reasonable solution for this problem we have studied the dehydration of glycerol in liquid phase using a supported HPA catalyst and developed an environmentally benign production of acrolein. Our method does not have any extreme conditions and produces a total conversion with high (93%) selectivity.
基金supported by the National Natural Science Foundation of China(No20873123)
文摘A series of MoTe_（0.15）V_（0.1）P_xO_n catalysts supported on the SiC were prepared by incipient wetness impregnation.The addition of P to MoTe_（0.15）V_（0.1）O_n/SiC catalysts improved the catalytic performance of selective oxidation from propane to acrolein（ACR）,and the catalyst showed highest selectivity（33.7%） and yield（10.7%） when x = 0.05.The MoTe_（0.15）V_（0.1）P_xO_n/SiC catalysts have been characterized by XRD,H_2-TPR,Raman,XPS and NH_3-TPD.The results indicated that a little H_3PMo_（12）O_（40） heteropoly acid and（VO）_2P_2O_7 formed and MoO_3 phase lessened after addition of P.The addition of P promoted the active species dispersed,increased the acidity on the surface,as well as might make the redox process easier.These significant differences improved the activity and selectivity of ACR.
基金Funded by the National Natural Science Foundation of China(No.21303154)
文摘The gas-phase dehydration of glycerol was conducted over HPW/MCM-41 catalysts,which were prepared by impregnation of different amount of H3PW（12）O（40）（HPW）on the MCM-41 support.The samples were characterized by XRD,N2 physisorption,FTIR,NH3-TPD,and pyridine-FTIR measurements.N2 physisorption results suggested that the uniform framework of MCM-41 could still be well maintained after modified with HPW.Pyridine-FTIR experiments indicate that HPW modified MCM-41 can generate rich Br？nsted acid sites.Moreover,Brnsted acid sites facilitated to improve acrolein selectivity.Under the optimized reaction conditions：40wt%HPW loading,20%glycerol concentration,and 320℃reaction temperature,the glycerol conversion and acrolein selectivity reach 85%and 80%,respectively.
基金Project supported by NSFC a.Department of Modern chemistry,University of Science and Technology of China.
文摘Photodecarbonylation reaction of acrolein at 193nm was investigated by ab initio molecular orbital method.Our result supports photodecarbonylation mechanisms proposed by Fujimoto,and predicts that the reaction should occur in ~3ππ potential energy surface prior to the ~1ππ potential energy surface.
基金supported by the Priority Academic Program Development of Jiangsu Higher Education Institutions and the Key Project of Jiangsu Commission of Health(Grant No.ZD2022012)。
文摘The circadian clock is crucial for the progression of cardiovascular diseases.Our previous studies showed that acrolein,an environmental pollutant,exacerbated atherosclerosis by reducing CLOCK/BMAL1 levels and disrupting circadian rhythm;in contrast,intermittent fasting(IF),a dietary regimen,ameliorated acrolein-induced atherosclerosis.In the current study,mice were administered acrolein at a dose of 3 mg/(kg·day)via drinking water and subjected to IF for 18 h(from 0:00 to 18:00).We observed that IF reduced the formation of aortic lesions accelerated by acrolein in Apo E-/-mice.Upon exposure to acrolein,the expression of Rel A,Il1b,and Tnf increased in the liver and heart tissues,but these changes were reversed by IF treatment.Notably,IF treatment upregulated the expression of adenosine monophosphate(AMP)-activated protein kinase catalytic subunit alpha-1(AMPKα1),p-AMPKα1,and sirtuin 1(SIRT1),while inhibiting acrolein-induced mitogen-activated protein kinase(MAPK)activation.Additionally,the expression of circadian genes Clock/Bmal1 was suppressed and disrupted by acrolein,whereas IF restored their expression.Moreover,consistent with the in vivo findings,shortterm starvation in vitro,as a fasting cell model,alleviated the dysregulation of CLOCK/BMAL1 and upregulated SIRT1 expression by modulating the AMPK and reactive oxygen species(ROS)-MAPK pathways activated by acrolein.In summary,we demonstrated that IF suppressed the ROS-MAPK pathway but activated the AMPK pathway to enhance the expression of circadian clock genes,thereby ameliorating acrolein-induced atherogenesis,which may shed light on strategies for preventing cardiovascular diseases.
文摘We report the first example of catalytic asymmetric Morita-Baylis-Hillman reaction of acrolein with aromatic aldehydes. The use of 10 mol% of Hatakeyama＇s catalyst β-isocupreidine C4, in combination with 20 mol% of 2,6-dimethoxybenzoic acid, could catalyze the reaction to give the desired products in up to 81% ee.
基金This work was supported by the National Institutes of Health(Grant#NS090244 and NS115094 to RS)as well as grants from the National Key Technology Support Program(2014BAI03B01 to Z.C)Sichuan International Science and Technology Innovation Cooperation Project(2020YFH0148 to Z.C).
文摘Background:The mechanisms underlying lesions of dopaminergic(DA)neurons,an essential pathology of Parkinson’s disease(PD),are largely unknown,although oxidative stress is recognized as a key factor.We have previously shown that the pro-oxidative aldehyde acrolein is a critical factor in PD pathology,and that acrolein scavenger hydralazine can reduce the elevated acrolein,mitigate DA neuron death,and alleviate motor deficits in a 6-hydroxydopamine(6-OHDA)rat model.As such,we hypothesize that a structurally distinct acrolein scavenger,dimercaprol(DP),can also offer neuroprotection and behavioral benefits.Methods:DP was used to lower the elevated levels of acrolein in the basal ganglia of 6-OHDA rats.The acrolein levels and related pathologies were measured by immunohistochemistry.Locomotor and behavioral effects of 6-OHDA injections and DP treatment were examined using the open field test and rotarod test.Pain was assessed using mechanical allodynia,cold hypersensitivity,and plantar tests.Finally,the effects of DP were assessed in vitro on SK-N-SH dopaminergic cells exposed to acrolein.Results:DP reduced acrolein and reversed the upregulation of pain-sensing transient receptor potential ankyrin 1(TRPA1)channels in the substantia nigra,striatum,and cortex.DP also mitigated both motor and sensory deficits typical of PD.In addition,DP lowered acrolein and protected DA-like cells in vitro.Acrolein’s ability to upregulate TRPA1 was also verified in vitro using cell lines.Conclusions:These results further elucidated the acrolein-mediated pathogenesis and reinforced the critical role of acrolein in PD while providing strong arguments for anti-acrolein treatments as a novel and feasible strategy to combat neurodegeneration in PD.Considering the extensive involvement of acrolein in various nervous system illnesses and beyond,anti-acrolein strategies may have wide applications and broad impacts on human health.
基金financially supported by the Research Fund for National Key R&D Program of China(No.2021YFA1501403)the National Natural Science Foundation of China(Nos.22038003,21922803,22178100,and 22208094)+2 种基金the Program of Shanghai Academic/Technology Research Leader(No.21XD1421000)the Shanghai Science and Technology Innovation Action Plan(No.22JC1403800)the Innovation Program of the Shanghai Municipal Education Commission.
文摘Propylene epoxidation by H_(2)and O_(2)to propylene oxide(PO)over the Au-Ti bifunctional catalysts,as an ideal reaction for PO production,has attracted great interest.Revealing the mechanism of acrolein formation is of great importance for understanding the mechanism of molecular oxygen activation and the formation of hydroperoxo species on the Au sites.Here,we investigate the reaction mechanism of propylene oxidation to acrolein on the Au/uncalcined TS-1(Au/TS-1-B)catalyst through a combination of multiple characterization,H_(2)/D_(2)exchange,kinetics experiment,and modeling.The Ti sites are found to be non-essential to acrolein formation.Moreover,the acrolein formation on the Au/TS-1-B catalyst is confirmed to be promoted by H_(2)through hydroperoxo species formation,which includes two main steps:propylene dehydrogenation to*C_(3)H_(5)with the aid of*OOH species,and*C_(3)H_(5)oxidation by*OOH to acrolein.The latter step is determined to be the rate-determining step because the corresponding kinetics model gives the best description for experimental results.This work not only provides kinetics insights for the propylene hydro-oxidation to acrolein on the Au-Ti bifunctional catalysts,but also facilitates the rational design of Au catalysts with high activity and selectivity in the direct propylene epoxidation with H_(2)and O_(2).
