首页 > 最新文献

ACS Omega最新文献

英文 中文
Corrosion and Electrolysis Mechanisms of Elemental Cobalt in NaCl Solution 单质钴在NaCl溶液中的腐蚀与电解机理
IF 4.1 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-04 DOI: 10.1021/acsomega.6c01299
Shengjiao Yang, Baochang Liu, Weiyi Yang, Hongxia Tan
To recycle/remove/protect the cobalt from polycrystalline diamond (PCD), hard alloys, and Co catalyst, this study investigates cobalt’s structural features, the inherent properties of the NaCl solution, and the interfacial chemistry at the solid–solution interface. For cobalt, the corrosion dependence on its structure is examined by X-ray diffraction (XRD), ultraviolet photoelectron spectroscopy (UPS), and density functional theory (DFT). In NaCl solution, properties─including dissolved oxygen (DO), electrical conductivity (EC), and viscosity─affect corrosion and electrolysis. Regarding interface science, the corrosion products (Co1.176(OH)2Cl0.348(H2O)0.456, β-Co(OH)2, and Co2(OH)3Cl) are identified through XRD and X-ray photoelectron spectroscopy (XPS). Chloride ions trigger the conversion of the β-Co(OH)2 pathway to the Co1.176(OH)2Cl0.348(H2O)0.456 and Co2(OH)3Cl pathways, a novel phenomenon in solid-solution corrosion. The residual rate (RR) of β-Co(OH)2, designated as RR(β-Co(OH)2), is originally defined to describe the transformation, which is detectable via electrochemical impedance spectroscopy (EIS) and modeled using a newly extended electrochemical element Wpc (based on the Finite-Length Warburg and Generalized Finite Warburg components) along with a novelly extended constant phase element (CPE) derived from the traditional CPE model. Furthermore, a new equivalent circuit model for EIS is developed to represent this conversion process in electrochemistry initially at an unstable solid-solution interface, and the concentration dependence of the effect caused by chloride ions is freshly revealed. This work also reveals other significant trends and mechanisms that depend on the NaCl solution concentration.
为了从聚晶金刚石(PCD)、硬质合金和Co催化剂中回收/去除/保护钴,本研究研究了钴的结构特征、NaCl溶液的固有性质以及固溶界面的化学性质。对于钴,通过x射线衍射(XRD)、紫外光电子能谱(UPS)和密度泛函理论(DFT)研究了腐蚀对其结构的依赖性。在NaCl溶液中,包括溶解氧(DO)、电导率(EC)和粘度在内的性能都会影响腐蚀和电解。界面科学方面,通过XRD和x射线光电子能谱(XPS)对腐蚀产物(Co1.176(OH)2Cl0.348(H2O)0.456、β-Co(OH)2和Co2(OH)3Cl)进行了鉴定。氯离子触发β-Co(OH)2途径转化为Co1.176(OH)2Cl0.348(H2O)0.456和Co2(OH)3Cl途径,这是固溶腐蚀中的一种新现象。β-Co(OH)2的剩余率(RR),称为RR(β-Co(OH)2),最初定义为描述转化,该转化可通过电化学阻抗谱(EIS)检测,并使用新扩展的电化学元件Wpc(基于有限长度Warburg和广义有限Warburg分量)以及衍生自传统CPE模型的新扩展的恒相元件(CPE)进行建模。此外,本文还建立了一个新的等效电路模型,用于描述在不稳定固-溶界面下电化学过程中的这种转化过程,并揭示了氯离子引起的效应的浓度依赖性。这项工作还揭示了依赖于NaCl溶液浓度的其他重要趋势和机制。
{"title":"Corrosion and Electrolysis Mechanisms of Elemental Cobalt in NaCl Solution","authors":"Shengjiao Yang, Baochang Liu, Weiyi Yang, Hongxia Tan","doi":"10.1021/acsomega.6c01299","DOIUrl":"https://doi.org/10.1021/acsomega.6c01299","url":null,"abstract":"To recycle/remove/protect the cobalt from polycrystalline diamond (PCD), hard alloys, and Co catalyst, this study investigates cobalt’s structural features, the inherent properties of the NaCl solution, and the interfacial chemistry at the solid–solution interface. For cobalt, the corrosion dependence on its structure is examined by X-ray diffraction (XRD), ultraviolet photoelectron spectroscopy (UPS), and density functional theory (DFT). In NaCl solution, properties─including dissolved oxygen (DO), electrical conductivity (EC), and viscosity─affect corrosion and electrolysis. Regarding interface science, the corrosion products (Co<sub>1.176</sub>(OH)<sub>2</sub>Cl<sub>0.348</sub>(H<sub>2</sub>O)<sub>0.456</sub>, β-Co(OH)<sub>2</sub>, and Co<sub>2</sub>(OH)<sub>3</sub>Cl) are identified through XRD and X-ray photoelectron spectroscopy (XPS). Chloride ions trigger the conversion of the β-Co(OH)<sub>2</sub> pathway to the Co<sub>1.176</sub>(OH)<sub>2</sub>Cl<sub>0.348</sub>(H<sub>2</sub>O)<sub>0.456</sub> and Co<sub>2</sub>(OH)<sub>3</sub>Cl pathways, a novel phenomenon in solid-solution corrosion. The residual rate (RR) of β-Co(OH)<sub>2</sub>, designated as RR(β-Co(OH)<sub>2</sub>), is originally defined to describe the transformation, which is detectable via electrochemical impedance spectroscopy (EIS) and modeled using a newly extended electrochemical element W<sub>pc</sub> (based on the Finite-Length Warburg and Generalized Finite Warburg components) along with a novelly extended constant phase element (CPE) derived from the traditional CPE model. Furthermore, a new equivalent circuit model for EIS is developed to represent this conversion process in electrochemistry initially at an unstable solid-solution interface, and the concentration dependence of the effect caused by chloride ions is freshly revealed. This work also reveals other significant trends and mechanisms that depend on the NaCl solution concentration.","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"199 1","pages":""},"PeriodicalIF":4.1,"publicationDate":"2026-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147371171","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}
引用次数: 0
Thermocatalytic Transformation of Nitriles Utilizing Pristine and Calcined ZnCr Layered Double Hydroxides for the Synthesis of Various Tetrazole- and Kynurenic Acid-Based Drug Candidates. 利用原始和煅烧的ZnCr层状双氢氧化物对腈的热催化转化合成各种四氮唑和Kynurenic酸基候选药物。
IF 4.3 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-04 eCollection Date: 2026-03-17 DOI: 10.1021/acsomega.5c12277
Hiba Alsoliman, Márton Szabados, Péter Bélteky, Zoltán Kónya, István Szatmári, Rebeka Mészáros

For the first time, Zn/Cr-containing layered double hydroxides (LDH) and mixed metal oxides (MMO) were applied in the synthesis of 5-substituted 1H-tetrazole heterocycles from different aromatic nitriles and TMSN3 (trimethylsilyl azide) as a less explosive/toxic and easily recoverable azide source. Effects of the nitrile concentration, reaction time, temperature, catalyst loading, and amount of N3 - source were carefully investigated to achieve high yields and selective tetrazole formation under the most sustainable conditions. Both Zn x Cr-LDH and -MMO (prepared based on thermogravimetric analysis) catalyst forms were efficient in the reaction (achieving between 60 and 95% conversion), and Zn3Cr-LDH tolerated nitriles containing different electron-withdrawing and -donating substituents well. The catalyst was recycled five times and characterized by X-ray diffractometry, transmission, and scanning electron microscopy with energy-dispersive X-ray analysis, infrared, and Raman spectroscopic techniques. Based on the tests, excellent catalyst reusability results (over 80% conversion and 100% selectivity even at the fifth use) were due to the robustness of the catalytic surface. The performance of zinc-rich Zn3Cr-LDH catalyst rivaled that of many extreme and noticeably expensive metal-containing materials (Cu, Pd, La), and it was also highly effective for use in DMSO solvent approved for medical research. For the extension of tetrazole synthesis, four new nitriles of kynurenic acid (glutamate receptor antagonists, potential neuroprotective agents with modified blood-brain barrier permeability) were synthesized and fully characterized by nuclear magnetic resonance and mass spectroscopic analyses.

本文首次将含Zn/ cr的层状双氢氧化物(LDH)和混合金属氧化物(MMO)应用于以不同芳香腈为原料合成5-取代1h -四氮杂环,并将三甲基硅基叠氮化物TMSN3作为一种低爆/毒性、易回收的叠氮化物源。研究了腈浓度、反应时间、温度、催化剂负载和N3源用量等因素对四氮唑合成的影响,以期在最可持续的条件下实现高收率和选择性生成四氮唑。Zn x Cr-LDH和-MMO(基于热重分析制备的)催化剂形式在反应中都是有效的(转化率在60%到95%之间),并且含有不同吸电子和供电子取代基的Zn3Cr-LDH耐受腈都很好。催化剂被回收了五次,并通过x射线衍射、透射、扫描电子显微镜、能量色散x射线分析、红外和拉曼光谱技术对其进行了表征。根据测试,优异的催化剂可重复使用效果(超过80%的转化率和100%的选择性,即使在第五次使用)是由于催化表面的坚固性。富锌的Zn3Cr-LDH催化剂的性能可与许多极端和非常昂贵的含金属材料(Cu, Pd, La)相媲美,并且在用于医学研究的DMSO溶剂中也非常有效。为了扩展四唑的合成,合成了四种新的犬尿酸腈(谷氨酸受体拮抗剂,具有改良血脑屏障通透性的潜在神经保护剂),并通过核磁共振和质谱分析对其进行了充分的表征。
{"title":"Thermocatalytic Transformation of Nitriles Utilizing Pristine and Calcined ZnCr Layered Double Hydroxides for the Synthesis of Various Tetrazole- and Kynurenic Acid-Based Drug Candidates.","authors":"Hiba Alsoliman, Márton Szabados, Péter Bélteky, Zoltán Kónya, István Szatmári, Rebeka Mészáros","doi":"10.1021/acsomega.5c12277","DOIUrl":"https://doi.org/10.1021/acsomega.5c12277","url":null,"abstract":"<p><p>For the first time, Zn/Cr-containing layered double hydroxides (LDH) and mixed metal oxides (MMO) were applied in the synthesis of 5-substituted 1<i>H</i>-tetrazole heterocycles from different aromatic nitriles and TMSN<sub>3</sub> (trimethylsilyl azide) as a less explosive/toxic and easily recoverable azide source. Effects of the nitrile concentration, reaction time, temperature, catalyst loading, and amount of N<sub>3</sub> <sup>-</sup> source were carefully investigated to achieve high yields and selective tetrazole formation under the most sustainable conditions. Both Zn <sub><i>x</i></sub> Cr-LDH and -MMO (prepared based on thermogravimetric analysis) catalyst forms were efficient in the reaction (achieving between 60 and 95% conversion), and Zn<sub>3</sub>Cr-LDH tolerated nitriles containing different electron-withdrawing and -donating substituents well. The catalyst was recycled five times and characterized by X-ray diffractometry, transmission, and scanning electron microscopy with energy-dispersive X-ray analysis, infrared, and Raman spectroscopic techniques. Based on the tests, excellent catalyst reusability results (over 80% conversion and 100% selectivity even at the fifth use) were due to the robustness of the catalytic surface. The performance of zinc-rich Zn<sub>3</sub>Cr-LDH catalyst rivaled that of many extreme and noticeably expensive metal-containing materials (Cu, Pd, La), and it was also highly effective for use in DMSO solvent approved for medical research. For the extension of tetrazole synthesis, four new nitriles of kynurenic acid (glutamate receptor antagonists, potential neuroprotective agents with modified blood-brain barrier permeability) were synthesized and fully characterized by nuclear magnetic resonance and mass spectroscopic analyses.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"11 10","pages":"16392-16405"},"PeriodicalIF":4.3,"publicationDate":"2026-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13000588/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147496870","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Synthesis and Characterization of Solvent-Complexes of per-Hydroxy Pillar[5]arene and Pillar[5]quinone: Experimental and Computational Insights 羟基柱[5]芳烃和柱[5]醌溶剂配合物的合成和表征:实验和计算见解
IF 4.1 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-04 DOI: 10.1021/acsomega.5c10756
Venkatesh Bollabathini, Quoc D. Ho, Eva Rauls, Kåre B. Jørgensen
When the macrocycles per-hydroxy pillar[5]arene (P[5]A–OH) and pillar[5]quinone (P[5]Q) are recrystallized from suitable solvents like acetone and 1,1,2,2-tetrachloroethane (TCE), respectively, the solvent molecules form host–guest complexes in a 1:2 stoichiometric ratio. These complexes survive prolonged exposure to vacuum at room temperature. Herein, we report improved yields for the preparation of 1,4-dimethoxypillar[5]arene (DMP[5]A) and its derivatives P[5]A–OH and P[5]Q, including detailed recrystallization procedures. The complexation behavior of these solvent molecules was investigated by 1H NMR and Infrared (IR) spectroscopy, interpreted with ab initio calculations. The ab initio calculations demonstrate that P[5]A–OH encapsulates two acetone molecules within its cavity, whereas P[5]Q binds with two TCE molecules outside the cavity. These complexes are stabilized by a combination of hydrogen bonding and CH−π interactions. IR spectroscopy confirmed the absorption of acetone by P[5]A–OH and displayed a blue-shifted C═O stretch (1779 vs 1727 cm–1 in free acetone) and red-shifted O–H modes (3384/3622 cm–1). Our charge transfer and structural analysis indicate that the C═O bond of acetone is contracted (1.24 Å→1.22 Å) due to enhanced polarization. For P[5]Q, TCE absorption is driven by hydrogen bonds, evidenced by the shift of C–H IR peaks near 3000 cm–1 and red-shifted C–Cl/C═O vibrations. Our study highlights the critical role of functional groups and noncovalent interactions in guest orientation, providing key insights for designing supramolecular materials.
当从丙酮和1,1,2,2-四氯乙烷(TCE)等合适的溶剂中分别重结晶大环羟基柱[5]芳烃(P[5] a - oh)和柱[5]醌(P[5]Q)时,溶剂分子以1:2的化学量比形成主客体配合物。这些复合物可以在室温下长时间暴露于真空中。本文报道了1,4-二甲氧基柱[5]芳烃(DMP[5]A)及其衍生物P[5]A - oh和P[5]Q的制备收率的提高,包括详细的再结晶过程。采用核磁共振氢谱(1H NMR)和红外光谱(IR)研究了这些溶剂分子的络合行为,并用从头计算进行了解释。从头计算表明,pb[5] A-OH在其空腔内封装了两个丙酮分子,而pb[5]q在空腔外与两个TCE分子结合。这些配合物通过氢键和CH−π相互作用的组合来稳定。红外光谱证实了P b[5] a - oh对丙酮的吸收,并显示了蓝移的C = O延伸(1779 vs 1727 cm-1)和红移的O - h模式(3384/3622 cm-1)。我们的电荷转移和结构分析表明,由于极化增强,丙酮的C = O键收缩(1.24 Å→1.22 Å)。对于pb[5]Q, TCE的吸收是由氢键驱动的,在3000 cm-1附近的C - h IR峰的位移和C - cl /C = O振动的红移证明了这一点。我们的研究强调了功能基团和非共价相互作用在客体取向中的关键作用,为设计超分子材料提供了关键见解。
{"title":"Synthesis and Characterization of Solvent-Complexes of per-Hydroxy Pillar[5]arene and Pillar[5]quinone: Experimental and Computational Insights","authors":"Venkatesh Bollabathini, Quoc D. Ho, Eva Rauls, Kåre B. Jørgensen","doi":"10.1021/acsomega.5c10756","DOIUrl":"https://doi.org/10.1021/acsomega.5c10756","url":null,"abstract":"When the macrocycles <i>per-</i>hydroxy pillar[5]arene (P[5]A–OH) and pillar[5]quinone (P[5]Q) are recrystallized from suitable solvents like acetone and 1,1,2,2-tetrachloroethane (TCE), respectively, the solvent molecules form host–guest complexes in a 1:2 stoichiometric ratio. These complexes survive prolonged exposure to vacuum at room temperature. Herein, we report improved yields for the preparation of 1,4-dimethoxypillar[5]arene (DMP[5]A) and its derivatives P[5]A–OH and P[5]Q, including detailed recrystallization procedures. The complexation behavior of these solvent molecules was investigated by <sup>1</sup>H NMR and Infrared (IR) spectroscopy, interpreted with <i>ab initio</i> calculations. The <i>ab initio</i> calculations demonstrate that P[5]A–OH encapsulates two acetone molecules within its cavity, whereas P[5]Q binds with two TCE molecules outside the cavity. These complexes are stabilized by a combination of hydrogen bonding and CH−π interactions. IR spectroscopy confirmed the absorption of acetone by P[5]A–OH and displayed a blue-shifted C═O stretch (1779 vs 1727 cm<sup>–1</sup> in free acetone) and red-shifted O–H modes (3384/3622 cm<sup>–1</sup>). Our charge transfer and structural analysis indicate that the C═O bond of acetone is contracted (1.24 Å→1.22 Å) due to enhanced polarization. For P[5]Q, TCE absorption is driven by hydrogen bonds, evidenced by the shift of C–H IR peaks near 3000 cm<sup>–1</sup> and red-shifted C–Cl/C═O vibrations. Our study highlights the critical role of functional groups and noncovalent interactions in guest orientation, providing key insights for designing supramolecular materials.","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"16 1","pages":""},"PeriodicalIF":4.1,"publicationDate":"2026-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147371170","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}
引用次数: 0
Stress-Induced Collapse and Reactivity of Nanobubbles in Water: Linking Pressure Dynamics to Interfacial Stability 水中纳米气泡的应力诱导崩塌和反应性:将压力动力学与界面稳定性联系起来
IF 4.1 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-04 DOI: 10.1021/acsomega.5c13561
Sowmya Atukuri, Lili Li, Jingru Wei, Shan Xue, Hui Wang, Feng Zhang, Yuning Yang, Zhihao Zhu, Taha Marhaba, Wen Zhang
Nanobubbles exhibit anomalous stability in water, yet their response to external mechanical stress remains poorly understood. Here, we examine how mechanical impact and centrifugal compression affect nanobubble stability, collapse, and interfacial reactivity. Nanobubbles of air, CO2, O2, H2, and N2 were generated in water and subjected to drop impacts (0–15 m) and centrifugation (0–15,000g). Bubble size and concentration were measured by nanoparticle tracking analysis, while dissolved oxygen and terephthalic acid fluorescence quantified gas loss and hydroxyl radical formation. Both stress modes reduced nanobubble concentrations by up to 40%, with nonmonotonic size changes indicating destabilization and partial collapse. Dissolved oxygen decreased by 6–8%, and radical generation followed CO2 > O2 > air > H2 > N2, demonstrating gas-dependent interfacial reactivity. Pressure-energy analysis showed that external pressures (104–107 Pa) and dissipated energies (10–12 kBT) match or exceed soft-particle eDLVO interaction barriers. These results show that nanobubble stability is governed by coupling.
纳米气泡在水中表现出异常的稳定性,但它们对外部机械应力的反应仍然知之甚少。在这里,我们研究了机械冲击和离心压缩如何影响纳米泡的稳定性、崩溃和界面反应性。在水中产生空气、CO2、O2、H2和N2的纳米气泡,并进行跌落冲击(0-15 m)和离心(0-15,000g)。通过纳米颗粒跟踪分析测量气泡大小和浓度,溶解氧和对苯二甲酸荧光定量气体损失和羟基自由基形成。两种应力模式都使纳米泡浓度降低了40%,其非单调的尺寸变化表明不稳定和部分崩溃。溶解氧减少6-8%,自由基生成顺序为CO2 >; O2 > air > H2 > N2,表现出气相依赖的界面反应性。压力-能量分析表明,外部压力(104-107 Pa)和耗散能量(10-12 kBT)符合或超过软粒子eDLVO相互作用势垒。这些结果表明,纳米气泡的稳定性受耦合作用的控制。
{"title":"Stress-Induced Collapse and Reactivity of Nanobubbles in Water: Linking Pressure Dynamics to Interfacial Stability","authors":"Sowmya Atukuri, Lili Li, Jingru Wei, Shan Xue, Hui Wang, Feng Zhang, Yuning Yang, Zhihao Zhu, Taha Marhaba, Wen Zhang","doi":"10.1021/acsomega.5c13561","DOIUrl":"https://doi.org/10.1021/acsomega.5c13561","url":null,"abstract":"Nanobubbles exhibit anomalous stability in water, yet their response to external mechanical stress remains poorly understood. Here, we examine how mechanical impact and centrifugal compression affect nanobubble stability, collapse, and interfacial reactivity. Nanobubbles of air, CO<sub>2</sub>, O<sub>2</sub>, H<sub>2</sub>, and N<sub>2</sub> were generated in water and subjected to drop impacts (0–15 m) and centrifugation (0–15,000<i>g</i>). Bubble size and concentration were measured by nanoparticle tracking analysis, while dissolved oxygen and terephthalic acid fluorescence quantified gas loss and hydroxyl radical formation. Both stress modes reduced nanobubble concentrations by up to 40%, with nonmonotonic size changes indicating destabilization and partial collapse. Dissolved oxygen decreased by 6–8%, and radical generation followed CO<sub>2</sub> &gt; O<sub>2</sub> &gt; air &gt; H<sub>2</sub> &gt; N<sub>2</sub>, demonstrating gas-dependent interfacial reactivity. Pressure-energy analysis showed that external pressures (10<sup>4</sup>–10<sup>7</sup> Pa) and dissipated energies (10–12 <i>k</i><sub>B</sub><i>T</i>) match or exceed soft-particle eDLVO interaction barriers. These results show that nanobubble stability is governed by coupling.","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"69 1","pages":""},"PeriodicalIF":4.1,"publicationDate":"2026-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147371204","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}
引用次数: 0
PEG/Folic Acid Coloaded Er:Y2O3 Upconversion Nanoparticles: Enhanced Internalization and Potential for High-Contrast Bioimaging in HCT-116 Cells. PEG/叶酸复合Er:Y2O3上转化纳米颗粒:增强内化和HCT-116细胞高对比度生物成像的潜力。
IF 4.3 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-04 eCollection Date: 2026-03-17 DOI: 10.1021/acsomega.6c00386
Ester Butera, Regina Maria Chiechio, Angela Caponnetto, Carmen Ferrara, Cinzia Di Pietro, Paolo Musumeci, Riccardo Reitano, Luca Lanzanò, Francesco Ruffino, Salvatore Petralia, Giovanni Arena, Carlotta Cosentino, Valerie Marchi, Annalinda Contino, Giuseppe Maccarrone

Erbium-doped yttrium oxide nanoparticles (Er:Y2O3 NPs) with a log-normal size distribution peaking at 43 nm were synthesized and coloaded with PEG and folic acid (FA) to achieve tumor cell targeting while maintaining good water dispersibility. Structural and optical analyses (TEM, FTIR, PL, upconversion) confirmed successful functionalization without significant alterations in the fluorescence signal. In colorectal cancer cells (HCT-116), MTT assays showed >80% viability for concentrations of NPs between 0.1 and 1 μg/mL, indicating low cytotoxicity. Confocal microscopy revealed fluorescence signals consistent with potential nanoparticle internalization, although contrast was limited by cellular autofluorescence. ICP-OES quantification supported greater internalization of PEG-FA nanoparticles compared to PEG nanoparticles, confirming the role of FA in enhancing internalization. Moreover, NIR excitation (980 nm) suppressed cellular autofluorescence, suggesting the potential of these nanoparticles for high-contrast bioimaging applications.

合成了对数正态分布在43 nm处的掺铒氧化钇纳米颗粒(Er:Y2O3 NPs),并与聚乙二醇和叶酸(FA)进行了负载,以实现肿瘤细胞靶向,同时保持良好的水分散性。结构和光学分析(TEM, FTIR, PL,上转换)证实了成功的功能化,荧光信号没有明显改变。在结直肠癌细胞(HCT-116)中,MTT实验显示,NPs浓度在0.1 ~ 1 μg/mL之间时,细胞存活率为bbb80 %,表明NPs具有低细胞毒性。共聚焦显微镜显示的荧光信号与潜在的纳米颗粒内化一致,尽管对比受到细胞自身荧光的限制。ICP-OES量化结果表明,与PEG纳米颗粒相比,PEG-FA纳米颗粒的内化程度更高,证实了FA在促进内化方面的作用。此外,近红外激发(980 nm)抑制细胞自身荧光,表明这些纳米颗粒具有高对比度生物成像应用的潜力。
{"title":"PEG/Folic Acid Coloaded Er:Y<sub>2</sub>O<sub>3</sub> Upconversion Nanoparticles: Enhanced Internalization and Potential for High-Contrast Bioimaging in HCT-116 Cells.","authors":"Ester Butera, Regina Maria Chiechio, Angela Caponnetto, Carmen Ferrara, Cinzia Di Pietro, Paolo Musumeci, Riccardo Reitano, Luca Lanzanò, Francesco Ruffino, Salvatore Petralia, Giovanni Arena, Carlotta Cosentino, Valerie Marchi, Annalinda Contino, Giuseppe Maccarrone","doi":"10.1021/acsomega.6c00386","DOIUrl":"https://doi.org/10.1021/acsomega.6c00386","url":null,"abstract":"<p><p>Erbium-doped yttrium oxide nanoparticles (Er:Y<sub>2</sub>O<sub>3</sub> NPs) with a log-normal size distribution peaking at 43 nm were synthesized and coloaded with PEG and folic acid (FA) to achieve tumor cell targeting while maintaining good water dispersibility. Structural and optical analyses (TEM, FTIR, PL, upconversion) confirmed successful functionalization without significant alterations in the fluorescence signal. In colorectal cancer cells (HCT-116), MTT assays showed >80% viability for concentrations of NPs between 0.1 and 1 μg/mL, indicating low cytotoxicity. Confocal microscopy revealed fluorescence signals consistent with potential nanoparticle internalization, although contrast was limited by cellular autofluorescence. ICP-OES quantification supported greater internalization of PEG-FA nanoparticles compared to PEG nanoparticles, confirming the role of FA in enhancing internalization. Moreover, NIR excitation (980 nm) suppressed cellular autofluorescence, suggesting the potential of these nanoparticles for high-contrast bioimaging applications.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"11 10","pages":"16936-16945"},"PeriodicalIF":4.3,"publicationDate":"2026-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13000564/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147496859","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Cryopreservation of Red-Blood-Cell-Derived Extracellular Vesicles. 红细胞来源的细胞外小泡的低温保存。
IF 4.3 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-04 eCollection Date: 2026-03-17 DOI: 10.1021/acsomega.5c10099
Kinga Ilyés, Tasvilla Sonallya, Judith Mihály, Anikó Gaál, Zoltán Varga

Extracellular vesicles (EVs) are crucial in many physiological and pathological processes, and therefore, they are increasingly studied for their potential as diagnostic biomarkers, therapeutic agents, and drug carriers. Red-blood-cell-derived EVs (REVs) have gained particular interest due to their beneficial properties for drug delivery and their unique biophysical and molecular characteristics, which make them a practical model system for EV research. While EV cryopreservation methods have advanced in the past decade, REVs remain relatively understudied, with their hemoglobin-rich composition presenting unique storage challenges. To address this gap, we investigated how the vesicle concentration and buffer composition affected REV preservation to identify the best storage conditions. We evaluated changes in protein and lipid contents, hemoglobin retention, particle recovery, size distribution, and optical properties using a variety of analytical methods. Our results show that phosphate-buffered saline (PBS), despite its common use, leads to significant losses in vesicle number and major compositional changes. While human serum albumin (HSA) alone showed no protective effect, the combined action of HEPES, HSA, and trehalose (PBS-HAT) preserved the biochemical and biophysical integrity of REVs much more effectively. Furthermore, we found that the initial REV concentration at the time of freezing significantly affected particle recovery but not the composition of the EVs. Notably, a loss in particle concentration (30%) was already evident at an initial concentration of 1.2 × 1011 particles/mL. Our findings demonstrate that PBS-HAT offers an effective strategy for the short- to midterm cryopreservation of REVs above the initial concentration of 1012 particles/mL.

细胞外囊泡(EVs)在许多生理和病理过程中都是至关重要的,因此,它们作为诊断生物标志物、治疗剂和药物载体的潜力越来越多地被研究。红细胞源性EV (REVs)由于其有益的药物传递特性和独特的生物物理和分子特性而获得了特别的关注,这使其成为EV研究的实用模型系统。虽然EV冷冻保存方法在过去十年中取得了进展,但rev的研究仍然相对不足,其富含血红蛋白的成分提出了独特的储存挑战。为了解决这一问题,我们研究了囊泡浓度和缓冲液成分对REV保存的影响,以确定最佳储存条件。我们使用多种分析方法评估了蛋白质和脂质含量、血红蛋白保留、颗粒恢复、尺寸分布和光学性质的变化。我们的研究结果表明,磷酸盐缓冲盐水(PBS)尽管被广泛使用,但会导致囊泡数量的显著减少和主要成分的变化。虽然单独使用人血清白蛋白(HSA)没有保护作用,但HEPES、HSA和海藻糖(PBS-HAT)的联合作用更有效地保护了REVs的生化和生物物理完整性。此外,我们发现冻结时的初始REV浓度显著影响颗粒回收率,但对电动汽车的组成没有影响。值得注意的是,在初始浓度为1.2 × 1011个颗粒/mL时,颗粒浓度的损失(30%)已经很明显。我们的研究结果表明,PBS-HAT为初始浓度为1012个颗粒/mL以上的rev提供了一种有效的中短期低温保存策略。
{"title":"Cryopreservation of Red-Blood-Cell-Derived Extracellular Vesicles.","authors":"Kinga Ilyés, Tasvilla Sonallya, Judith Mihály, Anikó Gaál, Zoltán Varga","doi":"10.1021/acsomega.5c10099","DOIUrl":"https://doi.org/10.1021/acsomega.5c10099","url":null,"abstract":"<p><p>Extracellular vesicles (EVs) are crucial in many physiological and pathological processes, and therefore, they are increasingly studied for their potential as diagnostic biomarkers, therapeutic agents, and drug carriers. Red-blood-cell-derived EVs (REVs) have gained particular interest due to their beneficial properties for drug delivery and their unique biophysical and molecular characteristics, which make them a practical model system for EV research. While EV cryopreservation methods have advanced in the past decade, REVs remain relatively understudied, with their hemoglobin-rich composition presenting unique storage challenges. To address this gap, we investigated how the vesicle concentration and buffer composition affected REV preservation to identify the best storage conditions. We evaluated changes in protein and lipid contents, hemoglobin retention, particle recovery, size distribution, and optical properties using a variety of analytical methods. Our results show that phosphate-buffered saline (PBS), despite its common use, leads to significant losses in vesicle number and major compositional changes. While human serum albumin (HSA) alone showed no protective effect, the combined action of HEPES, HSA, and trehalose (PBS-HAT) preserved the biochemical and biophysical integrity of REVs much more effectively. Furthermore, we found that the initial REV concentration at the time of freezing significantly affected particle recovery but not the composition of the EVs. Notably, a loss in particle concentration (30%) was already evident at an initial concentration of 1.2 × 10<sup>11</sup> particles/mL. Our findings demonstrate that PBS-HAT offers an effective strategy for the short- to midterm cryopreservation of REVs above the initial concentration of 10<sup>12</sup> particles/mL.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"11 10","pages":"16006-16016"},"PeriodicalIF":4.3,"publicationDate":"2026-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13000560/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147496929","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Recyclable Mn2O3@SiO2 Nanocatalyst for Selective Mono-N-alkylation of Amines Utilizing a Borrowing-Hydrogen Approach 可回收Mn2O3@SiO2纳米催化剂的选择性单n烷基化胺利用借用氢的方法
IF 4.1 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-04 DOI: 10.1021/acsomega.5c12338
Rajagopal Swaathy, Sambantham Karthikeyan
Amines are structural motifs that are found naturally in a wide variety of products and are used as fundamental building blocks in the production of pharmaceuticals and agrochemicals. The creation of C–N bonds has evolved; among many synthetic approaches, the utilization of the hydrogen-borrowing strategy has emerged as a green, atom-economical, and sustainable approach. This approach involves the N-alkylation of amines through the utilization of renewable alcohols as an alkylation source. In spite of the fact that there are a great number of heterogeneous catalysts based on nonnoble metals, the creation of systems that are highly active, stable, and recyclable continues to be a persistent challenge. In this article, we present the synthesis and catalytic application of a highly air-stable Mn2O3@SiO2 nanocomposite for the selective mono-N-alkylation of amines with alcohols, without any solvent, under a neat condition. Using the hydrogen-borrowing pathway, the catalyst effectively supports the alkylation reaction, which results in an excellent yield of N-alkylated products (up to 97%) within a period of 6 h. There was a demonstration of a broad substrate scope, which included a variety of functional groups and intermediates of amines that are relevant to the pharmaceutical industry. A comprehensive characterization of the nanocatalyst was carried out by employing techniques such as XRD, FT-IR, TGA, XPS, FE-SEM, TEM, and BET. The catalyst demonstrated outstanding reusability, as it maintained its activity over six successive catalytic cycles without suffering a substantial decline in performance. Control experiments were carried out to provide a mechanistic understanding, which supported the hypothesis of a borrowing-hydrogen pathway. The overall purpose of this protocol is to demonstrate a Mn2O3@SiO2 nanocatalytic system that is resilient, efficient, and recyclable for the purpose of achieving sustainable N-alkylation reactions.
胺是多种产品中天然存在的结构基序,是药品和农用化学品生产的基本组成部分。碳氮键的形成已经进化;在许多合成方法中,借用氢策略的利用已经成为一种绿色、原子经济和可持续的方法。这种方法涉及通过利用可再生醇作为烷基化源的胺的n -烷基化。尽管基于非贵金属的非均相催化剂数量众多,但创造高活性、稳定和可回收的系统仍然是一个持久的挑战。在本文中,我们介绍了一种高度空气稳定性的Mn2O3@SiO2纳米复合材料的合成和催化应用,用于胺与醇的选择性单n -烷基化,不需要任何溶剂,在整洁的条件下。利用借氢途径,催化剂有效地支持烷基化反应,从而在6小时内产生n-烷基化产物的优异收率(高达97%)。演示了广泛的底物范围,其中包括与制药工业相关的各种功能基团和胺的中间体。采用XRD、FT-IR、TGA、XPS、FE-SEM、TEM和BET等技术对纳米催化剂进行了全面表征。该催化剂表现出了出色的可重复使用性,因为它在连续六个催化循环中保持了活性,而性能没有明显下降。对照实验提供了一个机制的理解,这支持了一个借用氢途径的假设。该方案的总体目的是展示一个Mn2O3@SiO2纳米催化系统,该系统具有弹性,高效和可回收性,用于实现可持续的n -烷基化反应。
{"title":"Recyclable Mn2O3@SiO2 Nanocatalyst for Selective Mono-N-alkylation of Amines Utilizing a Borrowing-Hydrogen Approach","authors":"Rajagopal Swaathy, Sambantham Karthikeyan","doi":"10.1021/acsomega.5c12338","DOIUrl":"https://doi.org/10.1021/acsomega.5c12338","url":null,"abstract":"Amines are structural motifs that are found naturally in a wide variety of products and are used as fundamental building blocks in the production of pharmaceuticals and agrochemicals. The creation of C–N bonds has evolved; among many synthetic approaches, the utilization of the hydrogen-borrowing strategy has emerged as a green, atom-economical, and sustainable approach. This approach involves the N-alkylation of amines through the utilization of renewable alcohols as an alkylation source. In spite of the fact that there are a great number of heterogeneous catalysts based on nonnoble metals, the creation of systems that are highly active, stable, and recyclable continues to be a persistent challenge. In this article, we present the synthesis and catalytic application of a highly air-stable Mn<sub>2</sub>O<sub>3</sub>@SiO<sub>2</sub> nanocomposite for the selective mono-N-alkylation of amines with alcohols, without any solvent, under a neat condition. Using the hydrogen-borrowing pathway, the catalyst effectively supports the alkylation reaction, which results in an excellent yield of N-alkylated products (up to 97%) within a period of 6 h. There was a demonstration of a broad substrate scope, which included a variety of functional groups and intermediates of amines that are relevant to the pharmaceutical industry. A comprehensive characterization of the nanocatalyst was carried out by employing techniques such as XRD, FT-IR, TGA, XPS, FE-SEM, TEM, and BET. The catalyst demonstrated outstanding reusability, as it maintained its activity over six successive catalytic cycles without suffering a substantial decline in performance. Control experiments were carried out to provide a mechanistic understanding, which supported the hypothesis of a borrowing-hydrogen pathway. The overall purpose of this protocol is to demonstrate a Mn<sub>2</sub>O<sub>3</sub>@SiO<sub>2</sub> nanocatalytic system that is resilient, efficient, and recyclable for the purpose of achieving sustainable N-alkylation reactions.","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"81 1","pages":""},"PeriodicalIF":4.1,"publicationDate":"2026-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147371141","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}
引用次数: 0
Photoswitchable Activity of Mixed Bismuth Oxide (BiOx) for Water Splitting in Neutral Media 混合氧化铋(BiOx)在中性介质中水分解的光开关活性
IF 4.1 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-04 DOI: 10.1021/acsomega.5c10847
André Guimarães de Oliveira, Aparecida Cristina Mauro, Marcus Vinicius David, Ana Maria Rocco
Unary bismuth oxide (BiOx), containing both Bi3+ and Bi5+ species, exhibits a photoswitchable response that, to the best of our knowledge, has not yet been reported. The material has attracted increasing attention as an anode for the oxygen evolution reaction (OER), often in combination with additional elements to enhance electrochemical performance. This study investigates the electrodeposition of BiOx and its unexplored photoswitchable properties as an anode for solar-driven enhanced water splitting. Illumination with a xenon lamp equipped with solar simulation filters reduced the deposition time from 90 to 10 min without altering the amperometric profile, offering significant energy savings and potential for scale-up. Structural and morphological characterization were performed using scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS) and X-ray diffraction (XRD). Chopped light voltammetry revealed that the photocurrent in neutral media has a mixed photo- and electrocatalytic contribution. Under illumination, the BiOx electrode achieved a total current density of 2.5 mA cm–2, 140 mV lower than in dark conditions. Electrochemical impedance spectroscopy (EIS) revealed a decrease in depletion layer resistance with illumination, and an electrolyte-free impedance measurement indicated that changes in intrinsic conductivity also contribute to the PEC response. Overall, illumination enhances BiOx electrocatalytic water splitting, with a particularly pronounced effect on thin-layer films.
一元氧化铋(BiOx),包含Bi3+和Bi5+两种物质,表现出光开关响应,据我们所知,尚未有报道。该材料作为析氧反应(OER)的阳极越来越受到人们的关注,通常与其他元素结合以提高电化学性能。本研究研究了BiOx的电沉积及其未开发的光开关特性,作为太阳能驱动增强水分解的阳极。配备太阳模拟过滤器的氙灯照明将沉积时间从90分钟减少到10分钟,而不会改变安培曲线,从而显着节省能源并具有扩大规模的潜力。利用扫描电子显微镜、能量色散x射线能谱(SEM-EDS)和x射线衍射(XRD)对材料进行了结构和形态表征。斩波伏安法表明,中性介质中的光电流具有光催化和电催化的混合作用。在光照条件下,BiOx电极的总电流密度为2.5 mA cm-2,比黑暗条件下低140 mV。电化学阻抗谱(EIS)显示耗竭层电阻随光照降低,无电解质阻抗测量表明本征电导率的变化也有助于PEC响应。总的来说,光照增强了BiOx电催化水分解,对薄层薄膜的影响尤其明显。
{"title":"Photoswitchable Activity of Mixed Bismuth Oxide (BiOx) for Water Splitting in Neutral Media","authors":"André Guimarães de Oliveira, Aparecida Cristina Mauro, Marcus Vinicius David, Ana Maria Rocco","doi":"10.1021/acsomega.5c10847","DOIUrl":"https://doi.org/10.1021/acsomega.5c10847","url":null,"abstract":"Unary bismuth oxide (BiO<sub><i>x</i></sub>), containing both Bi<sup>3+</sup> and Bi<sup>5+</sup> species, exhibits a photoswitchable response that, to the best of our knowledge, has not yet been reported. The material has attracted increasing attention as an anode for the oxygen evolution reaction (OER), often in combination with additional elements to enhance electrochemical performance. This study investigates the electrodeposition of BiO<sub><i>x</i></sub> and its unexplored photoswitchable properties as an anode for solar-driven enhanced water splitting. Illumination with a xenon lamp equipped with solar simulation filters reduced the deposition time from 90 to 10 min without altering the amperometric profile, offering significant energy savings and potential for scale-up. Structural and morphological characterization were performed using scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS) and X-ray diffraction (XRD). Chopped light voltammetry revealed that the photocurrent in neutral media has a mixed photo- and electrocatalytic contribution. Under illumination, the BiO<sub><i>x</i></sub> electrode achieved a total current density of 2.5 mA cm<sup>–2</sup>, 140 mV lower than in dark conditions. Electrochemical impedance spectroscopy (EIS) revealed a decrease in depletion layer resistance with illumination, and an electrolyte-free impedance measurement indicated that changes in intrinsic conductivity also contribute to the PEC response. Overall, illumination enhances BiO<sub><i>x</i></sub> electrocatalytic water splitting, with a particularly pronounced effect on thin-layer films.","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"9 1","pages":""},"PeriodicalIF":4.1,"publicationDate":"2026-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147371134","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}
引用次数: 0
Atmospherically Stable Poly(Heptazine Imide) Composites 大气稳定聚七嗪亚胺复合材料
IF 4.1 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-04 DOI: 10.1021/acsomega.6c00037
Tatsushige Izumi, Ryoma Hayakawa, Momoka Isobe, Ryosuke Ohnuki, Yutaka Wakayama, Shinya Yoshioka, Kaname Kanai
Metal poly(heptazine imide) (MPHI), a two-dimensional carbon nitride polymer containing monovalent metal ions (M+), has recently attracted attention as a novel visible-light-driven photocatalyst. It exhibits photochromism, changing from yellow to blue-green upon light irradiation, regardless of the metal species, and is known to enhance ionic conductivity. Consequently, it has the potential to serve as a novel photoresponsive ionic conductor. However, the excited (color-changed) state that exhibits ionic conductivity is easily deactivated by atmospheric or dissolved oxygen in solution, making its application in actual devices challenging. Therefore, in this study, we developed a composite, protonated poly(heptazine imide) (HPHI):poly(vinyl alcohol) (PVA), by dispersing HPHI prepared by the acid treatment of potassium poly(heptazine imide) into a matrix of the insulating polymer PVA, which possesses high oxygen-blocking properties. HPHI:PVA can maintain a color-changed state for extended periods, even in air, while sustaining a low electrical resistance state. The time constant derived from the decay curve of HPHI:PVA’s absorbance over time is six times longer than that reported for HPHI composites using poly(methyl methacrylate) in previous studie. The duration of this color-changed state can be controlled by varying the degree of PVA saponification or temperature. Furthermore, a detailed investigation of the dependence of the electrical properties of HPHI:PVA on the percentage of HPHI revealed that proton conduction in HPHI:PVA arises from the percolation of poly(heptazine imide) particles within the composite. This finding also provides fundamental information regarding the ion-conduction mechanism in other MPHI composites. This study serves as an important guideline for the future development of new MPHI composites and applied research.
金属聚七嗪亚胺(MPHI)是一种含一价金属离子(M+)的二维氮化碳聚合物,近年来作为一种新型的可见光驱动光催化剂而受到广泛关注。它表现出光致变色,在光照射下从黄色变为蓝绿色,无论金属种类如何,并且已知可以增强离子电导率。因此,它具有作为一种新型光响应离子导体的潜力。然而,表现出离子电导率的激发态(变色)很容易被溶液中的大气或溶解氧钝化,这使得其在实际设备中的应用具有挑战性。因此,本研究将聚七嗪亚胺钾酸处理后的聚七嗪亚胺(HPHI)分散到具有高阻氧性能的绝缘聚合物PVA基体中,制备了质子化聚七嗪亚胺(HPHI):聚乙烯醇(PVA)复合材料。HPHI:PVA即使在空气中也能长时间保持变色状态,同时保持低电阻状态。由HPHI:PVA吸光度随时间的衰减曲线得出的时间常数比以往研究中使用聚甲基丙烯酸甲酯的HPHI复合材料的吸光度长6倍。这种变色状态的持续时间可以通过改变PVA皂化程度或温度来控制。此外,详细研究了HPHI:PVA的电学性质与HPHI百分比的关系,发现HPHI:PVA中的质子传导是由复合材料中聚(七乙胺亚胺)颗粒的渗透引起的。这一发现也为其他MPHI复合材料的离子传导机制提供了基础信息。该研究对未来新型MPHI复合材料的开发和应用研究具有重要的指导意义。
{"title":"Atmospherically Stable Poly(Heptazine Imide) Composites","authors":"Tatsushige Izumi, Ryoma Hayakawa, Momoka Isobe, Ryosuke Ohnuki, Yutaka Wakayama, Shinya Yoshioka, Kaname Kanai","doi":"10.1021/acsomega.6c00037","DOIUrl":"https://doi.org/10.1021/acsomega.6c00037","url":null,"abstract":"Metal poly(heptazine imide) (MPHI), a two-dimensional carbon nitride polymer containing monovalent metal ions (M<sup>+</sup>), has recently attracted attention as a novel visible-light-driven photocatalyst. It exhibits photochromism, changing from yellow to blue-green upon light irradiation, regardless of the metal species, and is known to enhance ionic conductivity. Consequently, it has the potential to serve as a novel photoresponsive ionic conductor. However, the excited (color-changed) state that exhibits ionic conductivity is easily deactivated by atmospheric or dissolved oxygen in solution, making its application in actual devices challenging. Therefore, in this study, we developed a composite, protonated poly(heptazine imide) (HPHI):poly(vinyl alcohol) (PVA), by dispersing HPHI prepared by the acid treatment of potassium poly(heptazine imide) into a matrix of the insulating polymer PVA, which possesses high oxygen-blocking properties. HPHI:PVA can maintain a color-changed state for extended periods, even in air, while sustaining a low electrical resistance state. The time constant derived from the decay curve of HPHI:PVA’s absorbance over time is six times longer than that reported for HPHI composites using poly(methyl methacrylate) in previous studie. The duration of this color-changed state can be controlled by varying the degree of PVA saponification or temperature. Furthermore, a detailed investigation of the dependence of the electrical properties of HPHI:PVA on the percentage of HPHI revealed that proton conduction in HPHI:PVA arises from the percolation of poly(heptazine imide) particles within the composite. This finding also provides fundamental information regarding the ion-conduction mechanism in other MPHI composites. This study serves as an important guideline for the future development of new MPHI composites and applied research.","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"15 1","pages":""},"PeriodicalIF":4.1,"publicationDate":"2026-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147371163","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}
引用次数: 0
Molecular Simulation Study of CO2 Adsorption and Sequestration on Clay Minerals under Geological Conditions 地质条件下粘土矿物对CO2吸附与封存的分子模拟研究
IF 4.1 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-04 DOI: 10.1021/acsomega.5c11645
Yongzhen Zheng, Meijun Li, Xiaoqiang Liu, Siyuan Zhang, Hong Xiao, Fali Shi, Surui Dong
Geological utilization and sequestration of CO2 are considered among the most effective methods for reducing carbon emissions. Clay minerals, as dominant diagenetic components in sedimentary formations, play a crucial role in CO2 geological sequestration owing to their large surface area and strong adsorption capacity. In this study, the adsorption and sequestration mechanisms of CO2 on typical clay minerals, including illite and kaolinite, were systematically investigated under geological temperature and pressure conditions representative of the eastern Junggar Basin using grand canonical Monte Carlo and molecular dynamics simulations. The results demonstrate that CO2 adsorption capacity is governed by the coupled effects of mineral type, pore size, temperature, and pressure. Illite exhibits approximately 1.4 times higher CO2 storage capacity than kaolinite, attributed to its stronger thermodynamic affinity and higher adsorption heat. Elevated temperature reduces CO2 adsorption, whereas increased pressure promotes it. In micropores smaller than 2 nm, confinement effects dominate and yield stable monolayer adsorption, while in mesopores, multilayer adsorption and coexistence of adsorbed and free CO2 phases occur as the pore size increases. The adsorbed phase proportion is consistently higher in illite, implying more stable and efficient CO2 trapping. These findings provide molecular-level insights into CO2-clay mineral interactions and establish a theoretical foundation for evaluating storage capacity, trapping stability, and caprock integrity, offering practical guidance for the safe and efficient implementation of CO2 geological sequestration projects in the eastern Junggar Basin, China.
地质利用和封存二氧化碳被认为是减少碳排放的最有效方法之一。黏土矿物作为沉积地层中主要的成岩组分,其表面积大、吸附能力强,在CO2地质封存中起着至关重要的作用。利用大正则蒙特卡罗模拟和分子动力学模拟,系统研究了准噶尔盆地东部具有代表性的地质温度和压力条件下,伊利石和高岭石等典型粘土矿物对CO2的吸附和封存机理。结果表明,CO2吸附能力受矿物类型、孔隙大小、温度和压力的耦合影响。由于伊利石具有更强的热力学亲和性和更高的吸附热,其CO2储存量约为高岭石的1.4倍。升高的温度减少二氧化碳的吸附,而增加的压力则促进二氧化碳的吸附。在小于2 nm的微孔中,约束效应起主导作用,产生稳定的单层吸附,而在中孔中,随着孔径的增大,吸附和自由CO2相出现多层吸附和共存。伊利石的吸附相比例一直较高,这意味着更稳定和有效的CO2捕获。这些发现为研究二氧化碳与黏土矿物的相互作用提供了分子水平的认识,为评价储层容量、圈闭稳定性和盖层完整性奠定了理论基础,为安全有效地实施准噶尔盆地东部地区的二氧化碳地质封存工程提供了实践指导。
{"title":"Molecular Simulation Study of CO2 Adsorption and Sequestration on Clay Minerals under Geological Conditions","authors":"Yongzhen Zheng, Meijun Li, Xiaoqiang Liu, Siyuan Zhang, Hong Xiao, Fali Shi, Surui Dong","doi":"10.1021/acsomega.5c11645","DOIUrl":"https://doi.org/10.1021/acsomega.5c11645","url":null,"abstract":"Geological utilization and sequestration of CO<sub>2</sub> are considered among the most effective methods for reducing carbon emissions. Clay minerals, as dominant diagenetic components in sedimentary formations, play a crucial role in CO<sub>2</sub> geological sequestration owing to their large surface area and strong adsorption capacity. In this study, the adsorption and sequestration mechanisms of CO<sub>2</sub> on typical clay minerals, including illite and kaolinite, were systematically investigated under geological temperature and pressure conditions representative of the eastern Junggar Basin using grand canonical Monte Carlo and molecular dynamics simulations. The results demonstrate that CO<sub>2</sub> adsorption capacity is governed by the coupled effects of mineral type, pore size, temperature, and pressure. Illite exhibits approximately 1.4 times higher CO<sub>2</sub> storage capacity than kaolinite, attributed to its stronger thermodynamic affinity and higher adsorption heat. Elevated temperature reduces CO<sub>2</sub> adsorption, whereas increased pressure promotes it. In micropores smaller than 2 nm, confinement effects dominate and yield stable monolayer adsorption, while in mesopores, multilayer adsorption and coexistence of adsorbed and free CO<sub>2</sub> phases occur as the pore size increases. The adsorbed phase proportion is consistently higher in illite, implying more stable and efficient CO<sub>2</sub> trapping. These findings provide molecular-level insights into CO<sub>2</sub>-clay mineral interactions and establish a theoretical foundation for evaluating storage capacity, trapping stability, and caprock integrity, offering practical guidance for the safe and efficient implementation of CO<sub>2</sub> geological sequestration projects in the eastern Junggar Basin, China.","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"59 1","pages":""},"PeriodicalIF":4.1,"publicationDate":"2026-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147371203","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}
引用次数: 0
期刊
ACS Omega
全部 Geobiology Appl. Clay Sci. Geochim. Cosmochim. Acta J. Hydrol. Org. Geochem. Carbon Balance Manage. Contrib. Mineral. Petrol. Int. J. Biometeorol. IZV-PHYS SOLID EART+ J. Atmos. Chem. Acta Oceanolog. Sin. Acta Geophys. ACTA GEOL POL ACTA PETROL SIN ACTA GEOL SIN-ENGL AAPG Bull. Acta Geochimica Adv. Atmos. Sci. Adv. Meteorol. Am. J. Phys. Anthropol. Am. J. Sci. Am. Mineral. Annu. Rev. Earth Planet. Sci. Appl. Geochem. Aquat. Geochem. Ann. Glaciol. Archaeol. Anthropol. Sci. ARCHAEOMETRY ARCT ANTARCT ALP RES Asia-Pac. J. Atmos. Sci. ATMOSPHERE-BASEL Atmos. Res. Aust. J. Earth Sci. Atmos. Chem. Phys. Atmos. Meas. Tech. Basin Res. Big Earth Data BIOGEOSCIENCES Geostand. Geoanal. Res. GEOLOGY Geosci. J. Geochem. J. Geochem. Trans. Geosci. Front. Geol. Ore Deposits Global Biogeochem. Cycles Gondwana Res. Geochem. Int. Geol. J. Geophys. Prospect. Geosci. Model Dev. GEOL BELG GROUNDWATER Hydrogeol. J. Hydrol. Earth Syst. Sci. Hydrol. Processes Int. J. Climatol. Int. J. Earth Sci. Int. Geol. Rev. Int. J. Disaster Risk Reduct. Int. J. Geomech. Int. J. Geog. Inf. Sci. Isl. Arc J. Afr. Earth. Sci. J. Adv. Model. Earth Syst. J APPL METEOROL CLIM J. Atmos. Oceanic Technol. J. Atmos. Sol. Terr. Phys. J. Clim. J. Earth Sci. J. Earth Syst. Sci. J. Environ. Eng. Geophys. J. Geog. Sci. Mineral. Mag. Miner. Deposita Mon. Weather Rev. Nat. Hazards Earth Syst. Sci. Nat. Clim. Change Nat. Geosci. Ocean Dyn. Ocean and Coastal Research npj Clim. Atmos. Sci. Ocean Modell. Ocean Sci. Ore Geol. Rev. OCEAN SCI J Paleontol. J. PALAEOGEOGR PALAEOCL PERIOD MINERAL PETROLOGY+ Phys. Chem. Miner. Polar Sci. Prog. Oceanogr. Quat. Sci. Rev. Q. J. Eng. Geol. Hydrogeol. RADIOCARBON Pure Appl. Geophys. Resour. Geol. Rev. Geophys. Sediment. Geol.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
现在去查看 取消
×
提示
确定
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:604180095
Book学术
文献互助 智能选刊 最新文献 互助须知 联系我们:info@booksci.cn
Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。
Copyright © 2023 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1