Neuroprotective drugs and selective monoamine oxidase inhibitors can slow down the progression and improve symptoms of Parkinson’s disease(PD).Since there is an implication of oxidative stress in the pathophysiologic...Neuroprotective drugs and selective monoamine oxidase inhibitors can slow down the progression and improve symptoms of Parkinson’s disease(PD).Since there is an implication of oxidative stress in the pathophysiological mechanisms of the disease,the compounds possessing an ability to reduce the oxidative stress are prime candidates for neuroprotection.Thereby our current study is focused on the development of new multi-target PD drugs capable of inhibiting the activity of monoamine oxidase-B while exerting neuroprotective and antioxidant properties.A small series of benzimidazole derivatives containing hydroxy and methoxy arylhydrazone fragments has been synthesized and the neurotoxicity of the compounds has been evaluated in vitro on neuroblastoma SH-SY5Y cells and on isolated rat brain synaptosomes by measuring the cell viability and the levels of reduced glutathione and a good safety profile has been shown.The 2-hydroxy-4-methoxy substituted arylhydrazone 7 was the least toxic on neuronal SH-SY5Y cells and showed the lowest neurotoxicity in rat brain synaptosomes.The neuroprotective properties of the test compounds were further assessed using two models:H2O2-induced oxidative stress on SH-SY5Y cells and 6-hydroxydopamine-induced neurotoxicity in rat brain synaptosomes.Compound 7 showed more pronounced neuroprotective activity on SH-SY5Y cells,compared to the referent melatonin and rasagiline.It also preserved the synaptosomal viability and the reduced glutathione levels;the effects were stronger than those of rasagiline and comparable to melatonin.All the tested compounds were capable to inhibit human monoamine oxidase-B enzyme to a significant extent,however,compound 7 exerted the most prominent inhibitory activity,similar to selegiline and rasagiline.The carried out molecular docking studies revealed that the activity is related to the appropriate molecular structure enabling the ligand to enter deeper in the narrow and highly lipophylic active site pocket of the human monoamine oxidase-B and has a favoring interaction with the key amino acid residues Tyr326 and Cys172.Since much scientific evidence points out the implication of iron dyshomeostasis in PD,the compounds were tested to reduce the ferrous iron induced oxidative molecular damage on biologically important molecules in an in vitro lecithin containing model system.All the investigated compounds denoted protection effect,stronger than the one of the referent melatonin.In order to support the assignments of the significant neuroprotective and antioxidant pharmacological activities,the radical-scavenging mechanisms of the most promising compound 7 were evaluated using DFT methods.It was found that the most probable free radicals scavenging mechanism in nonpolar phase is the hydrogen atom transfer from the amide group of compound 7,while in polar medium the process is expected to occur by a proton transfer.The current study outlines a perspective leading structure,bearing the potential for a new anti-PD drug.All performed procedures were approved by the Institutional Animal Care Committee of the Medical University of Sofia(Bulgarian Agency for Food Safety with Permission№190,approved on February 6,2020).展开更多
This work studied the structural effects of hematite(α-Fe2 O3), 2-line ferrihydrite(HFO) and goethite(α-FeOOH) on diethyl phthalate ester(DEP) degradation. The results showed that the degradation of DEP was faster u...This work studied the structural effects of hematite(α-Fe2 O3), 2-line ferrihydrite(HFO) and goethite(α-FeOOH) on diethyl phthalate ester(DEP) degradation. The results showed that the degradation of DEP was faster under 365 nm light irradiation than in the dark in the presence of iron(hydr)oxides. The apparent kinetic rates of DEP degradation followed the order HFO > goethite ≈ hematite in the dark and HFO > hematite > goethite under 365 nm light irradiation. Two pathways governed H2 O2 decomposition efficiency on iron(hydr)oxide surfaces:(1) forming UOH on inherent surface hydroxyl groups(Fe-OH) and(2) producing O2 and H2 O on the surface oxygen vacancies. X-ray photoelectron spectroscopy(XPS) analyses indicated that HFO not only has high Fe-OH content but also has high Vo content, resulting in its low H2 O2 utilization efficiency(η). DEP was degraded through hydrogen abstraction and deesterification, and the major products were(OH)2-DEP, mono-ethyl phthalate(MEP), OH-MEP,and phthalate acid(PA). The study is important in understanding the transformation of phthalate esters in top surface soils and surface waters under ultraviolet light.展开更多
Uniform and well-defined lanthanide hydroxide and oxide micro/nanorods Ln（OH）_3（Ln=La, Pr, Sm, Eu, Gd, Er） and Gd（OH）_3：Eu^（3＋）, Gd_2O_3：Eu^（3＋） were successfully synthesized through a green and facile h...Uniform and well-defined lanthanide hydroxide and oxide micro/nanorods Ln（OH）_3（Ln=La, Pr, Sm, Eu, Gd, Er） and Gd（OH）_3：Eu^（3＋）, Gd_2O_3：Eu^（3＋） were successfully synthesized through a green and facile hydrothermal method. Tetrabutylammonium hydroxide（TBAH） and lanthanide nitrides were used as the hydrothermal precursors without the addition of any templates/surfactants. The products were characterized by X-ray diffraction（XRD）, scanning electron microscopy（SEM）, transmission electron microscopy（TEM）, high-resolution transmission electron microscopy（HRTEM） and photoluminescence（PL） spectra. The result demonstrated that lanthanide hydroxide micro/nanorods with 20–80 nm in diameter and 50–450 in length were obtained. The size of the Ln（OH）_3（Ln=La, Pr, Sm, Eu, Gd, Er） rods increased with the increase of the atomic number. The size of the Gd（OH）_3：Eu^（3＋） rods decreased with the increase of p H value by modulating the amount of the TBAH solution. The as-formed product via the hydrothermal process, Gd（OH）_3：Eu^（3＋）, could be transformed to Gd_2O_3：Eu^（3＋） with the same morphology and a slight shrinking in size after a post annealing process. It is a facial method to synthesize photoluminescent nanomaterial of Gd_2O_3：Eu^（3＋）. The Gd_2O_3：Eu^（3＋） microrods exhibited strong red emission corresponding to ~5D）0→~7F_2 transition（610 nm） of Eu^（3＋） under UV light excitation（257 nm）.展开更多
A1-Fe （hydr）oxides with different A1/Fe molar ratios （4：1, 1：1, 1：4, 0：1） were prepared using a co- precipitation method and were then employed for simultaneous removal of arsenate and fluoride. The 4A1 ： Fe ...A1-Fe （hydr）oxides with different A1/Fe molar ratios （4：1, 1：1, 1：4, 0：1） were prepared using a co- precipitation method and were then employed for simultaneous removal of arsenate and fluoride. The 4A1 ： Fe was superior to other adsorbents for removal of arsenate and fluoride in the pH range of 5.0-9.0. The adsorption capacity of the A1-Fe （hydr）oxides for arsenate and fluoride at pH 6.50.3 increased with increasing A1 content in the adsorbents. The linear relationship between the amount of OH released from the adsorbent and the amount of arsenate or fluoride adsorbent by 4A1 ： Fe indicated that the adsorption of arsenate and fluoride by A1- Fe （hydr）oxides was realized primarily through quantita- tive ligand exchange. Moreover, there was a very good correlation between the surface hydroxyl group densities of A1-Fe （hydr）oxides and their adsorption capacities for arsenate or fluoride. The highest adsorption capacity for arsenate and fluoride by 4A1 ： Fe is mainly ascribed to its highest surface hydroxyl group density besides its largest pHpzc. The dosage of adsorbent necessary to remove arsenate and fluoride to meet the drinking water standard was mainly determined by the presence of fluoride since fluoride was generally present in groundwater at much higher concentration than arsenate.展开更多
The development of biochar-based granule-like adsorbents suitable for scaled-up application has been attracting increasing attention in the field of water treatment.Herein,a new formable porous granulated biochar load...The development of biochar-based granule-like adsorbents suitable for scaled-up application has been attracting increasing attention in the field of water treatment.Herein,a new formable porous granulated biochar loaded with La-Fe(hydr)oxides/montmorillonite(LaFe/MB)was fabricated via a granulation and pyrolysis process for enhanced phosphorus(P)removal from wastewater.Montmorillonite acted as a binder that increased the size of the granulated biochar,while the use of Fe promoted the surface charge and facilitated the dispersion of La,which was responsible for selective phosphate removal.LaFe/MB exhibited rapid phosphate adsorption kinetics and a high maximum adsorption capacity(Langmuir model,52.12 mg P g^(−1)),which were better than those of many existing granulated materials.The desorption and recyclability experiments showed that LaFe/MB could be regenerated,and maintained 76.7%of its initial phosphate adsorption capacity after four adsorption cycles.The high hydraulic endurance strength retention rate of the developed material(91.6%)suggested high practical applicability in actual wastewater.Electro-static attraction,surface precipitation,and inner-sphere complexation via ligand exchange were found to be involved in selective P removal over a wide pH range of 3-9.The thermodynamic parameters were determined,which revealed the feasibility and spontaneity of adsorption.Based on approximate site energy distribution analyses,high distribution frequency contributed to efficient P removal.The research results provide a new insight that LaFe/MB shows great application prospects for advanced phosphate removal from wastewater.展开更多
采用密度泛函理论(DFT)的计算方法,研究了铂催化2-烯炔基苯甲醛水合环化反应的微观机理及化学选择性的根源.计算结果表明,首先炔基被催化活化而发生亲核环化生成吡喃铂中间体;接着吡喃铂中间体与烯烃双键发生[3+2]环加成生成铂-碳卡宾...采用密度泛函理论(DFT)的计算方法,研究了铂催化2-烯炔基苯甲醛水合环化反应的微观机理及化学选择性的根源.计算结果表明,首先炔基被催化活化而发生亲核环化生成吡喃铂中间体;接着吡喃铂中间体与烯烃双键发生[3+2]环加成生成铂-碳卡宾复合物;之后,反应将沿2条路径进行,得到产物3a或4a,其中4a的生成需经两步水分子辅助的质子转移过程.生成产物3a需要克服的活化能垒为146.5 k J/mol;对4a的生成,烯醇式和酮式互变异构是决速步聚,当一个水分子参与反应时,对应的能垒为185.8 k J/mol,当2个和3个水分子参与反应时,能垒分别降低到128.1和64.9 k J/mol.因此,水分子参与催化得到产物4a的路径是有利的.另外,反应的选择性与在异构化过程中水的共催化作用有关.以上结果很好地解释了实验现象,并为铂催化水环化反应提供新的见解.展开更多
基金supported by the National Science Fund of Bulgaria(Young scientists project contract KП-06-М29/4to NA,MA,NHA,and DA).
文摘Neuroprotective drugs and selective monoamine oxidase inhibitors can slow down the progression and improve symptoms of Parkinson’s disease(PD).Since there is an implication of oxidative stress in the pathophysiological mechanisms of the disease,the compounds possessing an ability to reduce the oxidative stress are prime candidates for neuroprotection.Thereby our current study is focused on the development of new multi-target PD drugs capable of inhibiting the activity of monoamine oxidase-B while exerting neuroprotective and antioxidant properties.A small series of benzimidazole derivatives containing hydroxy and methoxy arylhydrazone fragments has been synthesized and the neurotoxicity of the compounds has been evaluated in vitro on neuroblastoma SH-SY5Y cells and on isolated rat brain synaptosomes by measuring the cell viability and the levels of reduced glutathione and a good safety profile has been shown.The 2-hydroxy-4-methoxy substituted arylhydrazone 7 was the least toxic on neuronal SH-SY5Y cells and showed the lowest neurotoxicity in rat brain synaptosomes.The neuroprotective properties of the test compounds were further assessed using two models:H2O2-induced oxidative stress on SH-SY5Y cells and 6-hydroxydopamine-induced neurotoxicity in rat brain synaptosomes.Compound 7 showed more pronounced neuroprotective activity on SH-SY5Y cells,compared to the referent melatonin and rasagiline.It also preserved the synaptosomal viability and the reduced glutathione levels;the effects were stronger than those of rasagiline and comparable to melatonin.All the tested compounds were capable to inhibit human monoamine oxidase-B enzyme to a significant extent,however,compound 7 exerted the most prominent inhibitory activity,similar to selegiline and rasagiline.The carried out molecular docking studies revealed that the activity is related to the appropriate molecular structure enabling the ligand to enter deeper in the narrow and highly lipophylic active site pocket of the human monoamine oxidase-B and has a favoring interaction with the key amino acid residues Tyr326 and Cys172.Since much scientific evidence points out the implication of iron dyshomeostasis in PD,the compounds were tested to reduce the ferrous iron induced oxidative molecular damage on biologically important molecules in an in vitro lecithin containing model system.All the investigated compounds denoted protection effect,stronger than the one of the referent melatonin.In order to support the assignments of the significant neuroprotective and antioxidant pharmacological activities,the radical-scavenging mechanisms of the most promising compound 7 were evaluated using DFT methods.It was found that the most probable free radicals scavenging mechanism in nonpolar phase is the hydrogen atom transfer from the amide group of compound 7,while in polar medium the process is expected to occur by a proton transfer.The current study outlines a perspective leading structure,bearing the potential for a new anti-PD drug.All performed procedures were approved by the Institutional Animal Care Committee of the Medical University of Sofia(Bulgarian Agency for Food Safety with Permission№190,approved on February 6,2020).
基金funded by the National Natural Science Foundation of China (No. 41773125)the Research Instrument Development Program of Chinese Academy of Sciences (No. YZ201638)the 135 Research Program of the Chinese Academy of Sciences (No. ISSASIP1620)
文摘This work studied the structural effects of hematite(α-Fe2 O3), 2-line ferrihydrite(HFO) and goethite(α-FeOOH) on diethyl phthalate ester(DEP) degradation. The results showed that the degradation of DEP was faster under 365 nm light irradiation than in the dark in the presence of iron(hydr)oxides. The apparent kinetic rates of DEP degradation followed the order HFO > goethite ≈ hematite in the dark and HFO > hematite > goethite under 365 nm light irradiation. Two pathways governed H2 O2 decomposition efficiency on iron(hydr)oxide surfaces:(1) forming UOH on inherent surface hydroxyl groups(Fe-OH) and(2) producing O2 and H2 O on the surface oxygen vacancies. X-ray photoelectron spectroscopy(XPS) analyses indicated that HFO not only has high Fe-OH content but also has high Vo content, resulting in its low H2 O2 utilization efficiency(η). DEP was degraded through hydrogen abstraction and deesterification, and the major products were(OH)2-DEP, mono-ethyl phthalate(MEP), OH-MEP,and phthalate acid(PA). The study is important in understanding the transformation of phthalate esters in top surface soils and surface waters under ultraviolet light.
基金Project supported by the Zhejiang Provincial Natural Science Foundation of China(LY14B010004)
文摘Uniform and well-defined lanthanide hydroxide and oxide micro/nanorods Ln（OH）_3（Ln=La, Pr, Sm, Eu, Gd, Er） and Gd（OH）_3：Eu^（3＋）, Gd_2O_3：Eu^（3＋） were successfully synthesized through a green and facile hydrothermal method. Tetrabutylammonium hydroxide（TBAH） and lanthanide nitrides were used as the hydrothermal precursors without the addition of any templates/surfactants. The products were characterized by X-ray diffraction（XRD）, scanning electron microscopy（SEM）, transmission electron microscopy（TEM）, high-resolution transmission electron microscopy（HRTEM） and photoluminescence（PL） spectra. The result demonstrated that lanthanide hydroxide micro/nanorods with 20–80 nm in diameter and 50–450 in length were obtained. The size of the Ln（OH）_3（Ln=La, Pr, Sm, Eu, Gd, Er） rods increased with the increase of the atomic number. The size of the Gd（OH）_3：Eu^（3＋） rods decreased with the increase of p H value by modulating the amount of the TBAH solution. The as-formed product via the hydrothermal process, Gd（OH）_3：Eu^（3＋）, could be transformed to Gd_2O_3：Eu^（3＋） with the same morphology and a slight shrinking in size after a post annealing process. It is a facial method to synthesize photoluminescent nanomaterial of Gd_2O_3：Eu^（3＋）. The Gd_2O_3：Eu^（3＋） microrods exhibited strong red emission corresponding to ~5D）0→~7F_2 transition（610 nm） of Eu^（3＋） under UV light excitation（257 nm）.
文摘A1-Fe （hydr）oxides with different A1/Fe molar ratios （4：1, 1：1, 1：4, 0：1） were prepared using a co- precipitation method and were then employed for simultaneous removal of arsenate and fluoride. The 4A1 ： Fe was superior to other adsorbents for removal of arsenate and fluoride in the pH range of 5.0-9.0. The adsorption capacity of the A1-Fe （hydr）oxides for arsenate and fluoride at pH 6.50.3 increased with increasing A1 content in the adsorbents. The linear relationship between the amount of OH released from the adsorbent and the amount of arsenate or fluoride adsorbent by 4A1 ： Fe indicated that the adsorption of arsenate and fluoride by A1- Fe （hydr）oxides was realized primarily through quantita- tive ligand exchange. Moreover, there was a very good correlation between the surface hydroxyl group densities of A1-Fe （hydr）oxides and their adsorption capacities for arsenate or fluoride. The highest adsorption capacity for arsenate and fluoride by 4A1 ： Fe is mainly ascribed to its highest surface hydroxyl group density besides its largest pHpzc. The dosage of adsorbent necessary to remove arsenate and fluoride to meet the drinking water standard was mainly determined by the presence of fluoride since fluoride was generally present in groundwater at much higher concentration than arsenate.
基金National Key Research and Development Program of China(2021YFD1700805)National Natural Science Foundation of China(41807132,22078136,41877090)the Jiangsu Province Agricultural Independent Innovation Fund(CX(19)2003).
文摘The development of biochar-based granule-like adsorbents suitable for scaled-up application has been attracting increasing attention in the field of water treatment.Herein,a new formable porous granulated biochar loaded with La-Fe(hydr)oxides/montmorillonite(LaFe/MB)was fabricated via a granulation and pyrolysis process for enhanced phosphorus(P)removal from wastewater.Montmorillonite acted as a binder that increased the size of the granulated biochar,while the use of Fe promoted the surface charge and facilitated the dispersion of La,which was responsible for selective phosphate removal.LaFe/MB exhibited rapid phosphate adsorption kinetics and a high maximum adsorption capacity(Langmuir model,52.12 mg P g^(−1)),which were better than those of many existing granulated materials.The desorption and recyclability experiments showed that LaFe/MB could be regenerated,and maintained 76.7%of its initial phosphate adsorption capacity after four adsorption cycles.The high hydraulic endurance strength retention rate of the developed material(91.6%)suggested high practical applicability in actual wastewater.Electro-static attraction,surface precipitation,and inner-sphere complexation via ligand exchange were found to be involved in selective P removal over a wide pH range of 3-9.The thermodynamic parameters were determined,which revealed the feasibility and spontaneity of adsorption.Based on approximate site energy distribution analyses,high distribution frequency contributed to efficient P removal.The research results provide a new insight that LaFe/MB shows great application prospects for advanced phosphate removal from wastewater.
基金supported by the National Natural Science Foundation of China(No.21433006)the Provincial Natural Science Foundation of Shandong,China(Nos.ZR2013BM026,2014ZRE27295)~~
文摘采用密度泛函理论(DFT)的计算方法,研究了铂催化2-烯炔基苯甲醛水合环化反应的微观机理及化学选择性的根源.计算结果表明,首先炔基被催化活化而发生亲核环化生成吡喃铂中间体;接着吡喃铂中间体与烯烃双键发生[3+2]环加成生成铂-碳卡宾复合物;之后,反应将沿2条路径进行,得到产物3a或4a,其中4a的生成需经两步水分子辅助的质子转移过程.生成产物3a需要克服的活化能垒为146.5 k J/mol;对4a的生成,烯醇式和酮式互变异构是决速步聚,当一个水分子参与反应时,对应的能垒为185.8 k J/mol,当2个和3个水分子参与反应时,能垒分别降低到128.1和64.9 k J/mol.因此,水分子参与催化得到产物4a的路径是有利的.另外,反应的选择性与在异构化过程中水的共催化作用有关.以上结果很好地解释了实验现象,并为铂催化水环化反应提供新的见解.
