Shuo Ai, Zhenhua Huang, Zhenhua Feng, Kaili Gao, Linghui Liu
For the controllable transformation of C3–6 diols in ethylene glycol (EG), H-Beta zeolite catalyst was modified with NH3 via incomplete desorption. 60.8% of acid sites on the zeolite were deactivated, but the ratio of strong acid sites was obviously increased. With 1,2-pentanediol (PDO) as a representative large-carbon-number diol, the undesirable acetalization and oligomerization reactions of EG were suppressed in the EG-PDO reaction system over the modified catalyst due to their dependency on total acid sites. NH3-TPD and FTIR results proved that Lewis acid sites on the modified zeolite were eliminated after modification, resulting in the suppression of acetalization and oligomerization reactions. In contrast, a portion of strong Brønsted acid sites still remained, ensuring the catalytic transformation of PDO. Only 8.2% of EG was consumed after 8-h reaction, and the conversion of PDO could reach 84.3%. The loading of NH3 on the surface of zeolite pores led to diffusion resistance, slightly decreasing the reaction rate of PDO without affecting the reaction selectivity. The catalytic reactions of other C3–6 diols in EG followed similar principles, and the selectivity to aldehydes or ketone was improved over this modified catalyst. Non-diol biomass hydrogenation products such as glycerol had negative influence on the selectivity, so these components should be isolated before the reactions. This catalyst could be reused at least 5 times, and the conversion of PDO slightly decreased. This work sheds light on the relationships between acid properties of catalyst and different reactions of diols.
{"title":"Controllable transformation of biomass-derived diols over ammonia-modified H-Beta zeolite","authors":"Shuo Ai, Zhenhua Huang, Zhenhua Feng, Kaili Gao, Linghui Liu","doi":"10.1039/d4nj02043j","DOIUrl":"https://doi.org/10.1039/d4nj02043j","url":null,"abstract":"For the controllable transformation of C<small><sub>3–6</sub></small> diols in ethylene glycol (EG), H-Beta zeolite catalyst was modified with NH<small><sub>3</sub></small> via incomplete desorption. 60.8% of acid sites on the zeolite were deactivated, but the ratio of strong acid sites was obviously increased. With 1,2-pentanediol (PDO) as a representative large-carbon-number diol, the undesirable acetalization and oligomerization reactions of EG were suppressed in the EG-PDO reaction system over the modified catalyst due to their dependency on total acid sites. NH3-TPD and FTIR results proved that Lewis acid sites on the modified zeolite were eliminated after modification, resulting in the suppression of acetalization and oligomerization reactions. In contrast, a portion of strong Brønsted acid sites still remained, ensuring the catalytic transformation of PDO. Only 8.2% of EG was consumed after 8-h reaction, and the conversion of PDO could reach 84.3%. The loading of NH<small><sub>3</sub></small> on the surface of zeolite pores led to diffusion resistance, slightly decreasing the reaction rate of PDO without affecting the reaction selectivity. The catalytic reactions of other C3–6 diols in EG followed similar principles, and the selectivity to aldehydes or ketone was improved over this modified catalyst. Non-diol biomass hydrogenation products such as glycerol had negative influence on the selectivity, so these components should be isolated before the reactions. This catalyst could be reused at least 5 times, and the conversion of PDO slightly decreased. This work sheds light on the relationships between acid properties of catalyst and different reactions of diols.","PeriodicalId":95,"journal":{"name":"New Journal of Chemistry","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141523817","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
We would like to take this opportunity to thank all of New Journal of Chemistry's reviewers for helping to preserve quality and integrity in chemical science literature. We would also like to highlight the Outstanding Reviewers for New Journal of Chemistry in 2023.
{"title":"Outstanding Reviewers for New Journal of Chemistry in 2023","authors":"","doi":"10.1039/d4nj90092h","DOIUrl":"https://doi.org/10.1039/d4nj90092h","url":null,"abstract":"We would like to take this opportunity to thank all of <em>New Journal of Chemistry</em>'s reviewers for helping to preserve quality and integrity in chemical science literature. We would also like to highlight the Outstanding Reviewers for <em>New Journal of Chemistry</em> in 2023.","PeriodicalId":95,"journal":{"name":"New Journal of Chemistry","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141523700","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Alexander Andreevich Buravlev, Alexander Makarov, Georgy E. Salnikov, Alexander Genaev, Irina Yu. Bagryanskaya, Pavel Viktorovich Nikulshin, Vyacheslav E. Platonov, Andrey Viktorovich Zibarev
New fluorinated dibenzo-1,2,5,6-tetrathiocines 1 and 2 were synthesized by a novel condensation of 1,2-disulfenyl chlorides under the influence of elemental Cu, and structurally defined in the solid state, solution, and gas phase by single-crystal XRD, variable-temperature 19F NMR and NOESY, and DFT calculations. Crystalline 1 and 2 exhibited the C2h chair and С2 twist molecular conformations, respectively. Unlike 1 displayed only C…S shortened intermolecular contacts, crystal structure of 2 featured F…π, F...F, F…S and S...S contacts. In toluene solutions at 296 K, both twist and chair conformers were observed in the ~1:1 and ~7:1 ratios for 1 and 2, respectively. For 1, the twist ↔ chair conformer interconversion was practically temperature-independent, and for 2 revealed ΔH ~3.5 kJ mol–1 and ΔS ~4.4 J K–1 mol–1. With DFT, the PESs for twist-chair transformation and twist-twist racemization were analyzed and the TSs exhibiting twist-halfchair and boat conformations, respectively, were found. Several additional stationary points on the PESs, corresponding to hidden intermediates and bifurcation points and featuring twistboat and halfchair conformations were detected. In chloroform solution under sunlight, 1 underwent 1,2,5,6-tetrathiocine → 1,2,3,6-tetrathiocine isomerization whose product was characterized by XRD.
{"title":"Synthesis, structural peculiarities, and photosensitivity of fluorinated dibenzo-1,2,5,6-tetrathiocines","authors":"Alexander Andreevich Buravlev, Alexander Makarov, Georgy E. Salnikov, Alexander Genaev, Irina Yu. Bagryanskaya, Pavel Viktorovich Nikulshin, Vyacheslav E. Platonov, Andrey Viktorovich Zibarev","doi":"10.1039/d4nj02284j","DOIUrl":"https://doi.org/10.1039/d4nj02284j","url":null,"abstract":"New fluorinated dibenzo-1,2,5,6-tetrathiocines 1 and 2 were synthesized by a novel condensation of 1,2-disulfenyl chlorides under the influence of elemental Cu, and structurally defined in the solid state, solution, and gas phase by single-crystal XRD, variable-temperature 19F NMR and NOESY, and DFT calculations. Crystalline 1 and 2 exhibited the C2h chair and С2 twist molecular conformations, respectively. Unlike 1 displayed only C…S shortened intermolecular contacts, crystal structure of 2 featured F…π, F...F, F…S and S...S contacts. In toluene solutions at 296 K, both twist and chair conformers were observed in the ~1:1 and ~7:1 ratios for 1 and 2, respectively. For 1, the twist ↔ chair conformer interconversion was practically temperature-independent, and for 2 revealed ΔH ~3.5 kJ mol–1 and ΔS ~4.4 J K–1 mol–1. With DFT, the PESs for twist-chair transformation and twist-twist racemization were analyzed and the TSs exhibiting twist-halfchair and boat conformations, respectively, were found. Several additional stationary points on the PESs, corresponding to hidden intermediates and bifurcation points and featuring twistboat and halfchair conformations were detected. In chloroform solution under sunlight, 1 underwent 1,2,5,6-tetrathiocine → 1,2,3,6-tetrathiocine isomerization whose product was characterized by XRD.","PeriodicalId":95,"journal":{"name":"New Journal of Chemistry","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141523928","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sergey P. Babailov, Mikhail Afonin, Nikolay Kompankov, Eduard S. Fomin
1H NMR measurements are reported for the C6D6 solution of the complex bis(tris(tert-butyl)cyclopentadienyl)neodymium(III) iodide [Cp'''2NdI] {where Cp''' = 1,3,4-tris(tert-butyl)cyclopentadienide}. Temperature dependences of the 1H NMR spectra of the complex have been analyzed using the bandshape analysis, taking into account the temperature variation of paramagnetic chemical shifts, within the frame of the dynamic NMR method. Conformational dynamics of the complex is conditioned by the process of racemization (with the value of the Gibbs activation energy ΔG≠298 = 58±3 kJ/mol). Due to substantial temperature dependence of paramagnetic shifts, the complex is essentially a NMR thermosensor reagent for local temperature monitoring. Good agreement between the calculated and experimental lanthanide-induced paramagnetic shifts in the 1H NMR spectra indicates the similarity of the structure of the complex in solution of C6D6 and the structure in the crystalline phase, found from the data of the X-ray structural study of the similar complex.
{"title":"Unexpected conformational dynamics associated with racemization in the [Cp'''2NdI] complex in solution {where Cp''' = 1,3,4-tris(tert-butyl)cyclopentadienide}","authors":"Sergey P. Babailov, Mikhail Afonin, Nikolay Kompankov, Eduard S. Fomin","doi":"10.1039/d4nj02185a","DOIUrl":"https://doi.org/10.1039/d4nj02185a","url":null,"abstract":"1H NMR measurements are reported for the C6D6 solution of the complex bis(tris(tert-butyl)cyclopentadienyl)neodymium(III) iodide [Cp'''2NdI] {where Cp''' = 1,3,4-tris(tert-butyl)cyclopentadienide}. Temperature dependences of the 1H NMR spectra of the complex have been analyzed using the bandshape analysis, taking into account the temperature variation of paramagnetic chemical shifts, within the frame of the dynamic NMR method. Conformational dynamics of the complex is conditioned by the process of racemization (with the value of the Gibbs activation energy ΔG≠298 = 58±3 kJ/mol). Due to substantial temperature dependence of paramagnetic shifts, the complex is essentially a NMR thermosensor reagent for local temperature monitoring. Good agreement between the calculated and experimental lanthanide-induced paramagnetic shifts in the 1H NMR spectra indicates the similarity of the structure of the complex in solution of C6D6 and the structure in the crystalline phase, found from the data of the X-ray structural study of the similar complex.","PeriodicalId":95,"journal":{"name":"New Journal of Chemistry","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141523812","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Aixin Cui, Man Wu, Tuo Guo, Xiunan Sun, Yulong Chen, Qingjie Guo
Hydrogenating CO2 to produce light olefins is a highly promising route for olefin synthesis. However, the premise of achieving a high yield is to develop a catalyst with a high conversion rate, selectivity, and stability. This paper reports a Ca2−xKxFe2O5 catalyst with an CO2 conversion of up to 46%, a light olefin selectivity of 34.59%, and an olefin-alkane molar ratio of 8.31. Ca addition increased the oxygen vacancy concentration and strong basic sites of the catalyst, resulting in improved HCOO* intermediate formation, better CO selectivity, and higher CO2 conversion rates. Meanwhile, the addition of K further enhanced the rate of CO2 conversion while also improving the selectivity of light olefins by promoting C–C coupling. Furthermore, the Ca1.0K1.0Fe2O5 catalyst demonstrated no notable deactivation over a period of 72 h, indicating the strong industrial potential of this catalyst.
氢化二氧化碳生产轻烯烃是一条极具前景的烯烃合成路线。然而，实现高产的前提是开发出一种具有高转化率、高选择性和高稳定性的催化剂。本文报告了一种 Ca2-xKxFe2O5 催化剂，其 CO2 转化率高达 46%，轻烯烃选择性为 34.59%，烯烃-烷烃摩尔比为 8.31。Ca 的加入增加了催化剂的氧空位浓度和强碱性位点，从而改善了 HCOO* 中间体的形成，提高了 CO 的选择性和 CO2 转化率。同时，K 的加入进一步提高了 CO2 转化率，并通过促进 C-C 偶联提高了轻烯烃的选择性。此外，Ca1.0K1.0Fe2O5 催化剂在 72 小时内没有出现明显的失活现象，这表明该催化剂具有很强的工业潜力。
{"title":"Potassium-modified calcium-ferrate-catalyzed hydrogenation of carbon dioxide to produce light olefins","authors":"Aixin Cui, Man Wu, Tuo Guo, Xiunan Sun, Yulong Chen, Qingjie Guo","doi":"10.1039/d4nj01579g","DOIUrl":"https://doi.org/10.1039/d4nj01579g","url":null,"abstract":"Hydrogenating CO<small><sub>2</sub></small> to produce light olefins is a highly promising route for olefin synthesis. However, the premise of achieving a high yield is to develop a catalyst with a high conversion rate, selectivity, and stability. This paper reports a Ca<small><sub>2−<em>x</em></sub></small>K<small><sub><em>x</em></sub></small>Fe<small><sub>2</sub></small>O<small><sub>5</sub></small> catalyst with an CO<small><sub>2</sub></small> conversion of up to 46%, a light olefin selectivity of 34.59%, and an olefin-alkane molar ratio of 8.31. Ca addition increased the oxygen vacancy concentration and strong basic sites of the catalyst, resulting in improved HCOO* intermediate formation, better CO selectivity, and higher CO<small><sub>2</sub></small> conversion rates. Meanwhile, the addition of K further enhanced the rate of CO<small><sub>2</sub></small> conversion while also improving the selectivity of light olefins by promoting C–C coupling. Furthermore, the Ca<small><sub>1.0</sub></small>K<small><sub>1.0</sub></small>Fe<small><sub>2</sub></small>O<small><sub>5</sub></small> catalyst demonstrated no notable deactivation over a period of 72 h, indicating the strong industrial potential of this catalyst.","PeriodicalId":95,"journal":{"name":"New Journal of Chemistry","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141531872","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The construction of heterojunctions is an effective strategy to improve the photogenerated carrier mobility rate and enhance the photocatalytic performance. The main bottlenecks in developing semiconductor photocatalysts lie in the poor light absorption and the fast recombination of photogenerated electron–hole pairs. In order to enhance the photocatalytic conversion of CO2, in this work, a kind of 2D/2D CuS/Ti3C2 heterostructure nanocomposites were designed. The formation of the heterojunction structure resulted in a significant enhancement of the light absorption range in the visible region of pristine Ti3C2 and a slight increase in the semiconductor bandgap width (2.58 eV), which in turn increased the generation of photogenerated electron–hole pairs and facilitated the acceleration of the carrier mobility efficiency, leading to a substantial improvement of the photocatalytic activity. After controlling the molar ratio of CuS/Ti3C2 at the optimum value of 1 : 8, the photocatalytic CO2 reduction conversion rate was the highest in the absence of co-catalysts. The yields of CO and CH4 were 10.68 and 25.21 μmol g−1 h−1, respectively, and were 5.51 and 3.15 times higher than that of pristine Ti3C2. Moreover, it resolved the bottleneck of the single CuS reduction product being only CO. In addition, the CuS/Ti3C2 (1 : 8) photocatalyst exhibited 35.07% selectivity and a C2H4 yield of 10.05 μmol g−1 h−1. The presence of large amounts of C1 and C2 intermediates on the catalyst surface was observed by in situ FTIR. Notably, after a cycling stability test lasting 40 h, the best samples retained 88.8% of the initial efficiency with good stability. This study further elucidates the mechanism of action and synergistic effects of CuS and Ti3C2 semiconductors in enhancing photoactivity.
{"title":"An in situ spectroscopic study of 2D CuS/Ti3C2 photocatalytic CO2 reduction to C1 and C2","authors":"Wanhe Li, Yahui Chen, Shuhan Jia, Yiying Zhou, Yiting Hua, Xinyu Lin, Zhi Zhu","doi":"10.1039/d4nj02327g","DOIUrl":"https://doi.org/10.1039/d4nj02327g","url":null,"abstract":"The construction of heterojunctions is an effective strategy to improve the photogenerated carrier mobility rate and enhance the photocatalytic performance. The main bottlenecks in developing semiconductor photocatalysts lie in the poor light absorption and the fast recombination of photogenerated electron–hole pairs. In order to enhance the photocatalytic conversion of CO<small><sub>2</sub></small>, in this work, a kind of 2D/2D CuS/Ti<small><sub>3</sub></small>C<small><sub>2</sub></small> heterostructure nanocomposites were designed. The formation of the heterojunction structure resulted in a significant enhancement of the light absorption range in the visible region of pristine Ti<small><sub>3</sub></small>C<small><sub>2</sub></small> and a slight increase in the semiconductor bandgap width (2.58 eV), which in turn increased the generation of photogenerated electron–hole pairs and facilitated the acceleration of the carrier mobility efficiency, leading to a substantial improvement of the photocatalytic activity. After controlling the molar ratio of CuS/Ti<small><sub>3</sub></small>C<small><sub>2</sub></small> at the optimum value of 1 : 8, the photocatalytic CO<small><sub>2</sub></small> reduction conversion rate was the highest in the absence of co-catalysts. The yields of CO and CH<small><sub>4</sub></small> were 10.68 and 25.21 μmol g<small><sup>−1</sup></small> h<small><sup>−1</sup></small>, respectively, and were 5.51 and 3.15 times higher than that of pristine Ti<small><sub>3</sub></small>C<small><sub>2</sub></small>. Moreover, it resolved the bottleneck of the single CuS reduction product being only CO. In addition, the CuS/Ti<small><sub>3</sub></small>C<small><sub>2</sub></small> (1 : 8) photocatalyst exhibited 35.07% selectivity and a C<small><sub>2</sub></small>H<small><sub>4</sub></small> yield of 10.05 μmol g<small><sup>−1</sup></small> h<small><sup>−1</sup></small>. The presence of large amounts of C1 and C2 intermediates on the catalyst surface was observed by <em>in situ</em> FTIR. Notably, after a cycling stability test lasting 40 h, the best samples retained 88.8% of the initial efficiency with good stability. This study further elucidates the mechanism of action and synergistic effects of CuS and Ti<small><sub>3</sub></small>C<small><sub>2</sub></small> semiconductors in enhancing photoactivity.","PeriodicalId":95,"journal":{"name":"New Journal of Chemistry","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141523819","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Natali de la Fuente Maldonado, Jin An Wang, Lifang Chen, Luis Enrique Noreña, A. Manzo-Robledo, Arel Guzmán, Julia Aguilar-Pliego, Julio González, Juan Navarrete-Bolaños, Dora Alicia Solís Casados
A number of phosphomolybdic acid dispersed on SBA-15 polyoxometalate catalysts with structural defects were synthesized and applied for the production of ultralow sulfur diesel. The oxygen defects in the catalysts were quantitatively determined by the Rietveld refinement method. These catalysts contained many surface acid sites including Brønsted (B) and Lewis (L) acid sites (648 to 1479 µmol/g), depending of the heteropolyacid content and the thermal treatment. The area under the IR absorption band at 980 cm-1 (the characteristic of the Mo=O bond) in the FTIR spectra of different catalysts was found to be inversely proportional to the variation of L acidity as a function of temperature, indicating that oxygen defects are the origin of the L acidity. In the oxidation reaction for removing dibenzothiophene, DBT, from a modal diesel, the DBT conversion correlated well with the oxygen defect concentration and total surface acidity, confirming that the surface acidity and oxygen defects played the key roles in DBT adsorption and oxidation. Almost 100% DBT conversion was achieved on the best 30wt%H3PMo12O40/SBA-15 catalyst under the optimal reaction condition (reaction time 60 min, reaction temperature 70°C, H2O2/DBT molar ratio 6-8, catalyst concentration 2-2.5 mg/mL, formic acid/H2O2 molar ratio 1.5). A novel mechanism of the DBT oxidative removal in a biphasic system involving the participation of the neighboring L and B acid sites, oxygen defect, and the formation of active polyoxometalates has been proposed.
合成了一些具有结构缺陷的磷钼酸分散在 SBA-15 聚氧化金属酸盐催化剂上，并将其用于生产超低硫柴油。催化剂中的氧缺陷通过里特维尔德细化法进行了定量测定。这些催化剂含有许多表面酸位点，包括布氏（B）酸位点和路易斯（L）酸位点（648 至 1479 µmol/g），具体取决于杂多酸含量和热处理方法。在不同催化剂的傅立叶变换红外光谱中，980 cm-1（Mo=O 键的特征）红外吸收带下的面积与 L 酸度随温度的变化成反比，这表明氧缺陷是 L 酸度的来源。在去除模态柴油中的二苯并噻吩（DBT）的氧化反应中，DBT 的转化率与氧缺陷浓度和总表面酸度密切相关，证实了表面酸度和氧缺陷在 DBT 吸附和氧化过程中起着关键作用。在最佳反应条件下（反应时间 60 分钟，反应温度 70°C，H2O2/DBT 摩尔比 6-8，催化剂浓度 2-2.5 mg/mL，甲酸/H2O2 摩尔比 1.5），30wt%H3PMo12O40/SBA-15 催化剂几乎实现了 100% 的 DBT 转化率。提出了一种在双相体系中氧化去除 DBT 的新机制，其中涉及邻近的 L 和 B 酸位点、氧缺陷以及活性多氧金属酸盐的形成。
{"title":"Ultralow sulfur diesel production with defective 12-molybdophosphoric acid polyoxometalate","authors":"Natali de la Fuente Maldonado, Jin An Wang, Lifang Chen, Luis Enrique Noreña, A. Manzo-Robledo, Arel Guzmán, Julia Aguilar-Pliego, Julio González, Juan Navarrete-Bolaños, Dora Alicia Solís Casados","doi":"10.1039/d4nj02368d","DOIUrl":"https://doi.org/10.1039/d4nj02368d","url":null,"abstract":"A number of phosphomolybdic acid dispersed on SBA-15 polyoxometalate catalysts with structural defects were synthesized and applied for the production of ultralow sulfur diesel. The oxygen defects in the catalysts were quantitatively determined by the Rietveld refinement method. These catalysts contained many surface acid sites including Brønsted (B) and Lewis (L) acid sites (648 to 1479 µmol/g), depending of the heteropolyacid content and the thermal treatment. The area under the IR absorption band at 980 cm-1 (the characteristic of the Mo=O bond) in the FTIR spectra of different catalysts was found to be inversely proportional to the variation of L acidity as a function of temperature, indicating that oxygen defects are the origin of the L acidity. In the oxidation reaction for removing dibenzothiophene, DBT, from a modal diesel, the DBT conversion correlated well with the oxygen defect concentration and total surface acidity, confirming that the surface acidity and oxygen defects played the key roles in DBT adsorption and oxidation. Almost 100% DBT conversion was achieved on the best 30wt%H3PMo12O40/SBA-15 catalyst under the optimal reaction condition (reaction time 60 min, reaction temperature 70°C, H2O2/DBT molar ratio 6-8, catalyst concentration 2-2.5 mg/mL, formic acid/H2O2 molar ratio 1.5). A novel mechanism of the DBT oxidative removal in a biphasic system involving the participation of the neighboring L and B acid sites, oxygen defect, and the formation of active polyoxometalates has been proposed.","PeriodicalId":95,"journal":{"name":"New Journal of Chemistry","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141523818","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Solid-state near-infrared (NIR) luminescence fluorophores have attracted much attention due to their potential in bio applications and advanced optical devices. Therefore, it is essential to design and synthesize novel NIR AIE fluorophores and investigating the structure-activity relationships for the applications. Here, we synthesized two NIR AIE o-carborane fluorophores with donor-acceptor-donor (D-A-D) structures. These fluorophores have emissions extending into the NIR region and are named CPO and CPS with phenoxazine (PXZ) and phenothiazine (PTZ) derivatives as the electron donors, respectively. Despite the very similar chemical structures of PXZ and PTZ, CPO and CPS exhibited rather different photophysical properties. The o-carborane fluorophores CPO and CPS show large Stokes shifts (> 14000 cm-1), near-infrared AIE characteristics, and self-recovering mechanochromic luminescence. The reorganization of molecular structures in the excited states leads to the planarization of their conjugated backbones and enhances Stokes shifts. This work not only demonstrates an efficient strategy for constructing organic NIR AIE o-carborane-containing fluorophores but also indicates their promising potential as advanced optoelectronic materials.
{"title":"Near-infrared Aggregation-Induced Emission Characteristics of New o-Carborane Fluorophores with Large Stokes Shifts and Self-recovering Mechanochromic Luminescence","authors":"Xueyan Wu, Na Li, Chenxi Zhang, Yan Lv, Jixi Guo","doi":"10.1039/d4nj01733a","DOIUrl":"https://doi.org/10.1039/d4nj01733a","url":null,"abstract":"Solid-state near-infrared (NIR) luminescence fluorophores have attracted much attention due to their potential in bio applications and advanced optical devices. Therefore, it is essential to design and synthesize novel NIR AIE fluorophores and investigating the structure-activity relationships for the applications. Here, we synthesized two NIR AIE o-carborane fluorophores with donor-acceptor-donor (D-A-D) structures. These fluorophores have emissions extending into the NIR region and are named CPO and CPS with phenoxazine (PXZ) and phenothiazine (PTZ) derivatives as the electron donors, respectively. Despite the very similar chemical structures of PXZ and PTZ, CPO and CPS exhibited rather different photophysical properties. The o-carborane fluorophores CPO and CPS show large Stokes shifts (> 14000 cm-1), near-infrared AIE characteristics, and self-recovering mechanochromic luminescence. The reorganization of molecular structures in the excited states leads to the planarization of their conjugated backbones and enhances Stokes shifts. This work not only demonstrates an efficient strategy for constructing organic NIR AIE o-carborane-containing fluorophores but also indicates their promising potential as advanced optoelectronic materials.","PeriodicalId":95,"journal":{"name":"New Journal of Chemistry","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141523820","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Youness El Bakri, Sabir Ali Siddique, Shaaban K. Mohamed, Muhammad Sarfraz, Hatem A. Abuelizz, Rashad Al-Salahi, Joel T. Mague, Eman A. Ahmed
Two new pyrazolidine-3,5-dione derivatives namely (Z)-4-(2-(4-bromophenyl)hydrazono)-1-phenylpyrazolidine-3,5-dione (2) and (E)-1-phenyl-4-((pyridin-2-ylamino)methylene)pyrazolidine-3,5-dione (3) were synthesized and their structures were elucidated by single-crystal X-ray analysis along with spectroscopic techniques. Density functional theory (DFT) studies were carried out to examine the distribution of charge, and natural bond orbital (NBO) analysis and frontier molecular orbital (FMO) analysis were carried out. Hirshfeld surface analysis was carried out to examine the intermolecular interactions, revealing a prevalence of H⋯H interactions in the crystals of both molecules. NBO analysis was carried out to investigate the stabilization energy, while MEP analysis was conducted to explore regions susceptible to nucleophilic and electrophilic attacks. The molecules were screened for their medicinal potential based on physiochemical and pharmacokinetics including (gastrointestinal) GI absorption, blood brain barrier (BBB) permeation, skin permeation capability, Caco-2 permeability, Madin–Darby canine kidney (MDCK) permeability, drug metabolism by the cytochrome P450 (CYP) family of liver enzymes, and toxicity evaluations. The expected metabolic reactions in the real cell system and the resulting metabolites along with their polarities for the determination of the probability of excretion from the body and drug-likeness were studied. To investigate the anticancer potency of 2 and 3, both were docked with three enzymes as drug targets for anticancer studies including HER2 (PDB ID: 3WSQ), EGFR (PDB ID: 5WB7), and the extracellular domain of the Tdp enzyme (PDB ID: 6N0D). From the calculated binding energies and inhibition constants, 2 is a better inhibitor of the target substrates than 3.
{"title":"Synthesis, investigation of the crystal structure, DFT calculations, and in silico medicinal potential of hydrazono- and aminomethylene substituted pyrazolidine-3,5-diones as potential anticancer scaffolds","authors":"Youness El Bakri, Sabir Ali Siddique, Shaaban K. Mohamed, Muhammad Sarfraz, Hatem A. Abuelizz, Rashad Al-Salahi, Joel T. Mague, Eman A. Ahmed","doi":"10.1039/d4nj01839g","DOIUrl":"https://doi.org/10.1039/d4nj01839g","url":null,"abstract":"Two new pyrazolidine-3,5-dione derivatives namely (<em>Z</em>)-4-(2-(4-bromophenyl)hydrazono)-1-phenylpyrazolidine-3,5-dione (<strong>2</strong>) and (<em>E</em>)-1-phenyl-4-((pyridin-2-ylamino)methylene)pyrazolidine-3,5-dione (<strong>3</strong>) were synthesized and their structures were elucidated by single-crystal X-ray analysis along with spectroscopic techniques. Density functional theory (DFT) studies were carried out to examine the distribution of charge, and natural bond orbital (NBO) analysis and frontier molecular orbital (FMO) analysis were carried out. Hirshfeld surface analysis was carried out to examine the intermolecular interactions, revealing a prevalence of H⋯H interactions in the crystals of both molecules. NBO analysis was carried out to investigate the stabilization energy, while MEP analysis was conducted to explore regions susceptible to nucleophilic and electrophilic attacks. The molecules were screened for their medicinal potential based on physiochemical and pharmacokinetics including (gastrointestinal) GI absorption, blood brain barrier (BBB) permeation, skin permeation capability, Caco-2 permeability, Madin–Darby canine kidney (MDCK) permeability, drug metabolism by the cytochrome P450 (CYP) family of liver enzymes, and toxicity evaluations. The expected metabolic reactions in the real cell system and the resulting metabolites along with their polarities for the determination of the probability of excretion from the body and drug-likeness were studied. To investigate the anticancer potency of <strong>2</strong> and <strong>3</strong>, both were docked with three enzymes as drug targets for anticancer studies including HER2 (PDB ID: 3WSQ), EGFR (PDB ID: 5WB7), and the extracellular domain of the Tdp enzyme (PDB ID: 6N0D). From the calculated binding energies and inhibition constants, <strong>2</strong> is a better inhibitor of the target substrates than <strong>3</strong>.","PeriodicalId":95,"journal":{"name":"New Journal of Chemistry","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141501268","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This study developed and utilized quantum dot conjugates labeled with antibodies (QDλ/Ab) to analyze the heterogeneity of cancer cell populations in co-cultured MCF-7/THP-1 cells, mimicking peripheral blood conditions. We synthesized QDλ with emissions at 450 nm, 525 nm, and 615 nm, confirmed by transmission electron microscopy and X-ray diffraction, suggesting distinct crystal structures and phase transitions. Surface modification with β-mercaptopropionic acid (QDλ/MPAb), polyethylene glycol (QDλ/MPA/PEG) and Streptaviding (QDλ/MPA/PEG/SA) enhanced biocompatibility and enabled specific antibody binding, as evidenced by consistent fluorescence and dynamic light scattering analyses. Flow cytometry and confocal microscopy validated the selective binding of antibodies to cancer markers and revealed significant heterogeneity within the cell populations. This study underscores the potential of QDλ/Ab conjugates in precise cancer biomarker detection and heterogeneity assessment.
{"title":"Deciphering Breast Cancer Cell Heterogeneity: A Quantum Dot-Conjugate Approach in MCF-7 and THP-1 Co-Cultures","authors":"Vasu Govardhana Reddy Peddiahgari, Vyshanava Satyanarayana Swamy, Surendra Babu Numbury, Obula Reddy Chittepu, Kamala Prasad Vasikarla, Anupalli Roja Rani, Muralidhararao Dowlathabad","doi":"10.1039/d4nj01990c","DOIUrl":"https://doi.org/10.1039/d4nj01990c","url":null,"abstract":"This study developed and utilized quantum dot conjugates labeled with antibodies (QDλ/Ab) to analyze the heterogeneity of cancer cell populations in co-cultured MCF-7/THP-1 cells, mimicking peripheral blood conditions. We synthesized QDλ with emissions at 450 nm, 525 nm, and 615 nm, confirmed by transmission electron microscopy and X-ray diffraction, suggesting distinct crystal structures and phase transitions. Surface modification with β-mercaptopropionic acid (QDλ/MPAb), polyethylene glycol (QDλ/MPA/PEG) and Streptaviding (QDλ/MPA/PEG/SA) enhanced biocompatibility and enabled specific antibody binding, as evidenced by consistent fluorescence and dynamic light scattering analyses. Flow cytometry and confocal microscopy validated the selective binding of antibodies to cancer markers and revealed significant heterogeneity within the cell populations. This study underscores the potential of QDλ/Ab conjugates in precise cancer biomarker detection and heterogeneity assessment.","PeriodicalId":95,"journal":{"name":"New Journal of Chemistry","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141523823","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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