Flavonoid glycoside scutellarin(SCU)has been widely applied in the treatment of cerebral ischemic diseases in China.In this article,we conducted research on the working mechanisms of SCU in hypoxia reoxygenation(HR)in...Flavonoid glycoside scutellarin(SCU)has been widely applied in the treatment of cerebral ischemic diseases in China.In this article,we conducted research on the working mechanisms of SCU in hypoxia reoxygenation(HR)injury of isolated cerebral basilar artery(BA)and erebral ischemia reperfusion(CIR)injury in rat models.In isolated rat BA rings,HR causes endothelial dysfunction(ED)and acetylcholine(ACh)induces endothelium-dependent vasodilation.The myography result showed that SCU(100μM)was able to significantly improve the endothelium-dependent vasodilation induced by Ach.However,SCU did not affect the ACh-induced relaxation in normal BA.Further studies suggested that SCU(10-1000μM)dose-dependently induced relaxation in isolated BA rings which were significantly blocked by the cGMP dependent protein kinase(PKG)inhibitor Rp-8-Br-cGMPs(PKGI-rp,4μM).Pre-incubation with SCU(500μM)reversed the impairment of endothelium-dependent vasodilation induced by HR,but the reversing effect was blocked if PKGI-rp(4μM)was added.The brain slice staining test in rats’model of middle cerebral artery occlusion(MCAO)induced CIR proved that the administration of SCU(45,90 mg/kg,iv)significantly reduced the area of cerebral infarction.The Western blot assay result showed that SCU(45 mg/kg,iv)increased brain PKG activity and PKG protein level after CIR surgery.In conclusion,our findings suggested that SCU possesses the ability of protecting brain cells against CIR injury through vascular endothelium protection and PKG signal.展开更多
Dry reforming of ethane(DRE)has received significant attention because of its potential to produce chemical raw materials and reduce carbon emissions.Herein,a composition-induced strong metal-support interaction(SMSI)...Dry reforming of ethane(DRE)has received significant attention because of its potential to produce chemical raw materials and reduce carbon emissions.Herein,a composition-induced strong metal-support interaction(SMSI)effect over FeNi/Al-Ce-O catalysts is revealed via X-ray photoelectron spectroscopy(XPS),H_(2)-temperature programmed reduction(TPR),and energy dispersive X-ray spectroscopy(EDS)elemental mapping.The introduction of Al into Al-Ce-O supports significantly influences the dispersion of surface active components and improves the catalytic performance for DRE over supported FeNi catalysts due to enhancement of the SMSI effect.The catalytic properties,for example,C_(2)H_(6) and CO_(2) conversion,CO selectivity and yield,and turnover frequencies(TOFs),of supported FeNi catalysts first increase and then decrease with increasing Al content,following the same trend as the theoretical effective surface area(TESA)of the corresponding catalysts.The FeNi/Ce-Al_(0.5) catalyst,with 50%Al content,exhibits the best DRE performance under steady-state conditions at 873 K.As observed by with in situ Fourier transform infrared spectroscopy(FTIR)analysis,the introduction of Al not only increases the content of surface Ce3+and oxygen vacancies but also promotes the dispersion of surface active components,which further alters the catalytic properties for DRE over supported FeNi catalysts.展开更多
Cr_(2)O_(3) has been recognized as a key oxide component in bifunctional catalysts to produce bridging intermediate,e.g.,methanol,from syngas.By combining density functional theory calculations and microkinetic modeli...Cr_(2)O_(3) has been recognized as a key oxide component in bifunctional catalysts to produce bridging intermediate,e.g.,methanol,from syngas.By combining density functional theory calculations and microkinetic modeling,we computationally studied the surface structures and catalytic activities of bare Cr_(2)O_(3)(001)and(012)surfaces,and two reduced(012)surfaces covered with dissociative hydrogens or oxygen vacancies.The reduction of(001)surface is much more difficult than that of(012)surface.The stepwise or the concerted reaction pathways were explored for the syngas to methanol conversion,and the hydrogenation of CO or CHO is identified as rate-determining step.Microkinetic modeling reveals that(001)surface is inactive for the reaction,and the rates of both reduced(012)surfaces(25−28 s^(-1))are about five times higher than bare(012)surface(4.3 s^(-1))at 673 K.These theoretical results highlight the importance of surface reducibility on the reaction and may provide some implications on the design of individual component in bifunctional catalysis.展开更多
The composition and evolution of interfacial species play a key role during electrocatalytic process.Unveiling the structural evolution and intermediate during catalytic process by in situ characterization can shed ne...The composition and evolution of interfacial species play a key role during electrocatalytic process.Unveiling the structural evolution and intermediate during catalytic process by in situ characterization can shed new light on the electrocatalytic reaction mechanism and develop highly efficient catalyst.However,directly probing the interfacial species is extremely difficult for most spectroscopic techniques due to complicated interfacial environment and ultra-low surface concentration.Herein,electrochemical core-shell nanoparticle enhanced Raman spectroscopy is utilized to probe the composition and evolution processes of interfacial species on Au@Pt,Au@Co,and Au@PtCo core-shell nanoparticle surfaces.The spectral evidences of interfacial intermediates including hydroxide radical(OH*),superoxide ion(O_(2)^(−)),as well as metal oxide species are directly captured by in situ Raman spectroscopy,which are further confirmed by the both isotopic experiment and density functional theory calculation.These results provide a mechanistic guideline for the rational design of highly efficient electrocatalysts.展开更多
It is a difficult challenge to simultaneously employ the cationic and anionic redox chemistry in cathode materials for sodium-ion batteries with high energy.Even though layered oxides(classified as two-dimensional oxi...It is a difficult challenge to simultaneously employ the cationic and anionic redox chemistry in cathode materials for sodium-ion batteries with high energy.Even though layered oxides(classified as two-dimensional oxides)demonstrate excellent promise in the high discharge capacity,their poor oxygen transformation via redox reactions is limited by crystal instability.Therefore,a doping strategy was conceived to tackle this issue and increase redox efficiency.K doping was applied to transform the two-dimensional Na_(1.3)Mn_(0.7)O_(2)(NMO)to threedimensional K_(0.2)Na_(1.3)Mn_(0.5)O_(2)(KNMO),preventing the irreversible phase shift and preserving the crystal structure’s stability while cycling.With this modification treatment,KNMO features manganese and oxygen reactive sites,delivering a promising energy density of 190mAh·g^(-1)at 5 mA·g^(-1)in the 2.0–4.5 V voltage range(vs71.4 mAh·g^(-1)for the pristine NMO).Moreover,it displays improved capacity retention of more than 83.5%after 50cycles at 50 mA·g^(-1).The results demonstrated that doped intercalation oxides were promising for redox oxygen transformation in sodium-ion batteries.展开更多
Background: Currently available evaluation criteria lbr penile tumescence and rigidity have been fraught with controversy. In tiffs study, we sought to establish normative Chinese evaluation criteria lbr penile tumes...Background: Currently available evaluation criteria lbr penile tumescence and rigidity have been fraught with controversy. In tiffs study, we sought to establish normative Chinese evaluation criteria lbr penile tumescence and rigidity by utilizing audiovisual sexual stimulation and RigiScanTM test (AVSS-Rigiscan test) with the administration of phosphodiesterase-5 inhibitor. Methods: A total of 1169 patients (aged 18-67 years) complained of erectile dysfunction (ED) underwent AVSS-RigiScan test with the administration of phosphodiesterase-5 inhibitor. A total of 1078 patients whose final etiological diagnosis was accurate by means of history, endocrine, vascular, and neurological diagnosis, International Index of Erectile Function 5 questionnaire, and erection hardness score were included in the research. Logistic regression model and receiver operating characteristic curve analysis were performed to determine the cutoffvalue of the RigiScanTM data. Then, the multivariable logistic analysis was used in the selected variables. Results: A normal restllt is defined as one erection with basal rigidity over 60% sustained for at least 8.75 rain, average event rigidity of tip at least 43.5% and base at least 50.5%, average maximum rigidity of tip at least 62.5% and base at least 67.5%, △tumescence (increase of tumescence or maxinaum-mininaum tumescence) of tip at least 1.75 cm and base at least 1.95 cm, total tumescence time at least 29.75 rain, and times of total tumescence at least once. Most importantly, basal rigidity over 60% sustained for at least 8.75 min, average event rigidity of tip at least 43.5%, and base at least 50.5% would be the new normative Chinese evaluation criteria for penile tumescence and rigidity. By multivariable logistic regression analysis, six significant RigiScanTM parameters including times of total tumescence, duration of erectile episodes over 60%, average event rigidity of tip, Atumescence of tip, average event rigidity of base, and Atunaescence of base contribute to the risk model of ED. In logistic regression equation, predict value P 〈 0.303 was considered as psychogenic ED. The sensitivity and specificity of the AVSS-RigiScan test with the administration ofphosphodiesterase-5 inhibitor in discriminating psychogenic from organic ED was 87.7% and 93.4%,, respectively. Conclusions: This study suggests that AVSS-RigiScan test with oral phosphodiesterase-5 inhibitors can objectively assess penile tumescence and rigidity and seems to be a better modality in differentiating psychogenic from organic ED. ttowever, due to the limited sample size, bias cannot be totally excluded.展开更多
Objective: To investigate the antagonistic cell injury effect and molecular mechanism of scutellarin(SCU)in hypoxia reoxygenation(HR) treated human cardiac microvascular endothelial cells(HCMECs).Methods: The method o...Objective: To investigate the antagonistic cell injury effect and molecular mechanism of scutellarin(SCU)in hypoxia reoxygenation(HR) treated human cardiac microvascular endothelial cells(HCMECs).Methods: The method of 12 h hypoxia following by 12 h reoxygenation was used to culture HCMECs in vitro to built cell injury model. The groups were divided into control group, model(HR) group, and HR + SCU(0.1 μmol/L, 1 μmol/L, and 10 μmol/L) group. The cell viability was determined by MTT, and oxidative stress was detected by malondialdehyde(MDA) levels by biochemical assay kit. Protein expression of JAK2/p-JAK2 and STAT3/p-STAT3 were evaluated by Western blot.Results: The results of MTT and MDA showed that HR decreased the cell viability(P < 0.05) and increased MDA level significantly(P < 0.05), SCU played a contrary role in these processes. Western blot analysis indicates that, the expression of JAK2 and p-JAK2, STAT3, and p-STAT3 were increased in model group when compared with control group(P < 0.05); Compared with model group, their expression were reduced by SCU(P < 0.05).Conclusion: SCU took a protective effect on HR-treated HCMECs, and the molecular mechanism may be associated with the inhibition of JAK2/STAT3 signal transduction pathway.展开更多
Summaryof main observation and conclusion Understanding and optimizing structure of active sites is of significance in zeolite catalysis.Benzene ethylation is an industrially important process catalyzed by H-MCM-22 ze...Summaryof main observation and conclusion Understanding and optimizing structure of active sites is of significance in zeolite catalysis.Benzene ethylation is an industrially important process catalyzed by H-MCM-22 zeolite;while the active sites still remain elusive.In this work,density functional theory(DFT)calculations were employed to investigate the benzene ethylation at two different types of Br?nsted acid sites(BAS)in H-MCM-22 zeolite,namely the internal cavity(IC)acid site and the external surface(ES)acid site.Both the stepwise and concerted pathways were addressed.The compari-son of the calculated energetics of two pathways indicates that the benzene ethylation reaction primarily proceeds via the concerted pathway at both the IC and ES acid sites of H-MCM-22.The calculated overall Gibbs free energies at reaction condition(473 K and 3.5 MPa)on the IC and ES acid sites are 90 and 86 kJ/mol,with the rate constants of 1.20×10^3and 2.92×10^3s^-1,respectively.It indicates that benzene ethylation could occur both on the IC and ES acid sites,with the catalytic activity of IC acid site being slightly lower than that of ES acid site.Furthermore,we theoretically reveal that the acid strength at the ES site is slightly weaker than that at the IC site via the frequency shift after the adsorption of CO.The differences in dispersion interaction between ES and IC sites are also quantified by the adsorption of base molecules with different sizes.The calculated results in this work demonstrate that the acid sites at the external surface of H-MCM-22 zeolites are suitable for benzene ethylation to produce ethylbenzene,providing theoretical implications for tailoring the distribution of active sites in H-MCM-22 zeolite.展开更多
基金the National Natural Science Foundation of China(Nos.81560589,30960450,81173110 and 81560072)Yunnan Provincial Science and Technology Department(Nos.202105AF150015,202102AA310030,2018FE001(-026),2017FE467(-019),2014BC012,and 2017IC041)Yunnan Provincial Educational Department(Nos.2018JS161).
文摘Flavonoid glycoside scutellarin(SCU)has been widely applied in the treatment of cerebral ischemic diseases in China.In this article,we conducted research on the working mechanisms of SCU in hypoxia reoxygenation(HR)injury of isolated cerebral basilar artery(BA)and erebral ischemia reperfusion(CIR)injury in rat models.In isolated rat BA rings,HR causes endothelial dysfunction(ED)and acetylcholine(ACh)induces endothelium-dependent vasodilation.The myography result showed that SCU(100μM)was able to significantly improve the endothelium-dependent vasodilation induced by Ach.However,SCU did not affect the ACh-induced relaxation in normal BA.Further studies suggested that SCU(10-1000μM)dose-dependently induced relaxation in isolated BA rings which were significantly blocked by the cGMP dependent protein kinase(PKG)inhibitor Rp-8-Br-cGMPs(PKGI-rp,4μM).Pre-incubation with SCU(500μM)reversed the impairment of endothelium-dependent vasodilation induced by HR,but the reversing effect was blocked if PKGI-rp(4μM)was added.The brain slice staining test in rats’model of middle cerebral artery occlusion(MCAO)induced CIR proved that the administration of SCU(45,90 mg/kg,iv)significantly reduced the area of cerebral infarction.The Western blot assay result showed that SCU(45 mg/kg,iv)increased brain PKG activity and PKG protein level after CIR surgery.In conclusion,our findings suggested that SCU possesses the ability of protecting brain cells against CIR injury through vascular endothelium protection and PKG signal.
基金support from the National Key Research and Development Program of China(2017YFB0702800)the China Petrochemical Corporation(Sinopec Group)the National Natural Science Foundation of China(91434102 and U1663221)。
文摘Dry reforming of ethane(DRE)has received significant attention because of its potential to produce chemical raw materials and reduce carbon emissions.Herein,a composition-induced strong metal-support interaction(SMSI)effect over FeNi/Al-Ce-O catalysts is revealed via X-ray photoelectron spectroscopy(XPS),H_(2)-temperature programmed reduction(TPR),and energy dispersive X-ray spectroscopy(EDS)elemental mapping.The introduction of Al into Al-Ce-O supports significantly influences the dispersion of surface active components and improves the catalytic performance for DRE over supported FeNi catalysts due to enhancement of the SMSI effect.The catalytic properties,for example,C_(2)H_(6) and CO_(2) conversion,CO selectivity and yield,and turnover frequencies(TOFs),of supported FeNi catalysts first increase and then decrease with increasing Al content,following the same trend as the theoretical effective surface area(TESA)of the corresponding catalysts.The FeNi/Ce-Al_(0.5) catalyst,with 50%Al content,exhibits the best DRE performance under steady-state conditions at 873 K.As observed by with in situ Fourier transform infrared spectroscopy(FTIR)analysis,the introduction of Al not only increases the content of surface Ce3+and oxygen vacancies but also promotes the dispersion of surface active components,which further alters the catalytic properties for DRE over supported FeNi catalysts.
基金This work was supported by the National Natural Science Foundation of China(No.92045303)the China Postdoctoral Science Foundation(No.2020M681444).The computational resources from Sinopec Geophysical Research Institute are acknowledged.
文摘Cr_(2)O_(3) has been recognized as a key oxide component in bifunctional catalysts to produce bridging intermediate,e.g.,methanol,from syngas.By combining density functional theory calculations and microkinetic modeling,we computationally studied the surface structures and catalytic activities of bare Cr_(2)O_(3)(001)and(012)surfaces,and two reduced(012)surfaces covered with dissociative hydrogens or oxygen vacancies.The reduction of(001)surface is much more difficult than that of(012)surface.The stepwise or the concerted reaction pathways were explored for the syngas to methanol conversion,and the hydrogenation of CO or CHO is identified as rate-determining step.Microkinetic modeling reveals that(001)surface is inactive for the reaction,and the rates of both reduced(012)surfaces(25−28 s^(-1))are about five times higher than bare(012)surface(4.3 s^(-1))at 673 K.These theoretical results highlight the importance of surface reducibility on the reaction and may provide some implications on the design of individual component in bifunctional catalysis.
基金the National Key Research and Development Program of China(No.2020YFB1505800)the National Natural Science Foundation of China(Nos.21925404 and 22021001)+5 种基金the Shenzhen Science and Technology Research Grant(No.JCYJ20200109140416788)the Science and Technology Program of Fujian Province(No.2021Y01010295)the Youth Talent Support Program of Fujian Province(Eyas Plan of Fujian Province 2021)Research Initiation Fund of Jimei University(No.ZQ2021008)the Natural Science Foundation of Fujian Province of China(No.2021J06001)the China Postdoctoral Science Foundation(Nos.2021TQ0188 and 2021M691874).
文摘The composition and evolution of interfacial species play a key role during electrocatalytic process.Unveiling the structural evolution and intermediate during catalytic process by in situ characterization can shed new light on the electrocatalytic reaction mechanism and develop highly efficient catalyst.However,directly probing the interfacial species is extremely difficult for most spectroscopic techniques due to complicated interfacial environment and ultra-low surface concentration.Herein,electrochemical core-shell nanoparticle enhanced Raman spectroscopy is utilized to probe the composition and evolution processes of interfacial species on Au@Pt,Au@Co,and Au@PtCo core-shell nanoparticle surfaces.The spectral evidences of interfacial intermediates including hydroxide radical(OH*),superoxide ion(O_(2)^(−)),as well as metal oxide species are directly captured by in situ Raman spectroscopy,which are further confirmed by the both isotopic experiment and density functional theory calculation.These results provide a mechanistic guideline for the rational design of highly efficient electrocatalysts.
基金financially supported by the Scientific Research Startup Fund for Shenzhen High-Caliber Personnel of SZPT(No.6021310029K)Research Projects of Department of Education of Guangdong Province(No.2023KTSCX319)。
文摘It is a difficult challenge to simultaneously employ the cationic and anionic redox chemistry in cathode materials for sodium-ion batteries with high energy.Even though layered oxides(classified as two-dimensional oxides)demonstrate excellent promise in the high discharge capacity,their poor oxygen transformation via redox reactions is limited by crystal instability.Therefore,a doping strategy was conceived to tackle this issue and increase redox efficiency.K doping was applied to transform the two-dimensional Na_(1.3)Mn_(0.7)O_(2)(NMO)to threedimensional K_(0.2)Na_(1.3)Mn_(0.5)O_(2)(KNMO),preventing the irreversible phase shift and preserving the crystal structure’s stability while cycling.With this modification treatment,KNMO features manganese and oxygen reactive sites,delivering a promising energy density of 190mAh·g^(-1)at 5 mA·g^(-1)in the 2.0–4.5 V voltage range(vs71.4 mAh·g^(-1)for the pristine NMO).Moreover,it displays improved capacity retention of more than 83.5%after 50cycles at 50 mA·g^(-1).The results demonstrated that doped intercalation oxides were promising for redox oxygen transformation in sodium-ion batteries.
文摘Background: Currently available evaluation criteria lbr penile tumescence and rigidity have been fraught with controversy. In tiffs study, we sought to establish normative Chinese evaluation criteria lbr penile tumescence and rigidity by utilizing audiovisual sexual stimulation and RigiScanTM test (AVSS-Rigiscan test) with the administration of phosphodiesterase-5 inhibitor. Methods: A total of 1169 patients (aged 18-67 years) complained of erectile dysfunction (ED) underwent AVSS-RigiScan test with the administration of phosphodiesterase-5 inhibitor. A total of 1078 patients whose final etiological diagnosis was accurate by means of history, endocrine, vascular, and neurological diagnosis, International Index of Erectile Function 5 questionnaire, and erection hardness score were included in the research. Logistic regression model and receiver operating characteristic curve analysis were performed to determine the cutoffvalue of the RigiScanTM data. Then, the multivariable logistic analysis was used in the selected variables. Results: A normal restllt is defined as one erection with basal rigidity over 60% sustained for at least 8.75 rain, average event rigidity of tip at least 43.5% and base at least 50.5%, average maximum rigidity of tip at least 62.5% and base at least 67.5%, △tumescence (increase of tumescence or maxinaum-mininaum tumescence) of tip at least 1.75 cm and base at least 1.95 cm, total tumescence time at least 29.75 rain, and times of total tumescence at least once. Most importantly, basal rigidity over 60% sustained for at least 8.75 min, average event rigidity of tip at least 43.5%, and base at least 50.5% would be the new normative Chinese evaluation criteria for penile tumescence and rigidity. By multivariable logistic regression analysis, six significant RigiScanTM parameters including times of total tumescence, duration of erectile episodes over 60%, average event rigidity of tip, Atumescence of tip, average event rigidity of base, and Atunaescence of base contribute to the risk model of ED. In logistic regression equation, predict value P 〈 0.303 was considered as psychogenic ED. The sensitivity and specificity of the AVSS-RigiScan test with the administration ofphosphodiesterase-5 inhibitor in discriminating psychogenic from organic ED was 87.7% and 93.4%,, respectively. Conclusions: This study suggests that AVSS-RigiScan test with oral phosphodiesterase-5 inhibitors can objectively assess penile tumescence and rigidity and seems to be a better modality in differentiating psychogenic from organic ED. ttowever, due to the limited sample size, bias cannot be totally excluded.
基金funded by the National Natural Science Foundation of China(Grant No.30960450,No.81560589,and No.81173110)Yunnan Province Science and Technology Department and Education Department(Grant No.2017FE467(-019),No.2018JS161,No.2014FA010,No.ZD2015009)Yunnan–USA joint research center of molecular medicines(No.2015ID001)
文摘Objective: To investigate the antagonistic cell injury effect and molecular mechanism of scutellarin(SCU)in hypoxia reoxygenation(HR) treated human cardiac microvascular endothelial cells(HCMECs).Methods: The method of 12 h hypoxia following by 12 h reoxygenation was used to culture HCMECs in vitro to built cell injury model. The groups were divided into control group, model(HR) group, and HR + SCU(0.1 μmol/L, 1 μmol/L, and 10 μmol/L) group. The cell viability was determined by MTT, and oxidative stress was detected by malondialdehyde(MDA) levels by biochemical assay kit. Protein expression of JAK2/p-JAK2 and STAT3/p-STAT3 were evaluated by Western blot.Results: The results of MTT and MDA showed that HR decreased the cell viability(P < 0.05) and increased MDA level significantly(P < 0.05), SCU played a contrary role in these processes. Western blot analysis indicates that, the expression of JAK2 and p-JAK2, STAT3, and p-STAT3 were increased in model group when compared with control group(P < 0.05); Compared with model group, their expression were reduced by SCU(P < 0.05).Conclusion: SCU took a protective effect on HR-treated HCMECs, and the molecular mechanism may be associated with the inhibition of JAK2/STAT3 signal transduction pathway.
基金The authors acknowledge the financial support from the Na-tional Key Research and Development Program of China(No.2017YFB0702800)the National Natural Science Foundation of China(No.21673295).The computational resources from Sinopec Geophysical Research Institute are acknowledged.
文摘Summaryof main observation and conclusion Understanding and optimizing structure of active sites is of significance in zeolite catalysis.Benzene ethylation is an industrially important process catalyzed by H-MCM-22 zeolite;while the active sites still remain elusive.In this work,density functional theory(DFT)calculations were employed to investigate the benzene ethylation at two different types of Br?nsted acid sites(BAS)in H-MCM-22 zeolite,namely the internal cavity(IC)acid site and the external surface(ES)acid site.Both the stepwise and concerted pathways were addressed.The compari-son of the calculated energetics of two pathways indicates that the benzene ethylation reaction primarily proceeds via the concerted pathway at both the IC and ES acid sites of H-MCM-22.The calculated overall Gibbs free energies at reaction condition(473 K and 3.5 MPa)on the IC and ES acid sites are 90 and 86 kJ/mol,with the rate constants of 1.20×10^3and 2.92×10^3s^-1,respectively.It indicates that benzene ethylation could occur both on the IC and ES acid sites,with the catalytic activity of IC acid site being slightly lower than that of ES acid site.Furthermore,we theoretically reveal that the acid strength at the ES site is slightly weaker than that at the IC site via the frequency shift after the adsorption of CO.The differences in dispersion interaction between ES and IC sites are also quantified by the adsorption of base molecules with different sizes.The calculated results in this work demonstrate that the acid sites at the external surface of H-MCM-22 zeolites are suitable for benzene ethylation to produce ethylbenzene,providing theoretical implications for tailoring the distribution of active sites in H-MCM-22 zeolite.