Chemphyschem最新文献

Exploring the Photophysical Processes of an Al³⁺ Sensor Based on Schiff Base. 席夫碱Al3+传感器的光物理过程研究。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-07-04 DOI: 10.1002/cphc.202500196

Bingqing Sun, Haoyang Song, Yi Nan, Lei Liu, Juyoung Yoon

{"title":"Exploring the Photophysical Processes of an Al3+ Sensor Based on Schiff Base.","authors":"Bingqing Sun, Haoyang Song, Yi Nan, Lei Liu, Juyoung Yoon","doi":"10.1002/cphc.202500196","DOIUrl":"https://doi.org/10.1002/cphc.202500196","url":null,"abstract":"Schiff bases are commonly used as building blocks in the development of turn-on sensors for Al3+ detection. The isomerization of the CN bond in Schiff bases is generally believed to induce fluorescence quenching. Inhibiting this isomerization process through interactions with the target ion, Al3+, enhances fluorescence, enabling its detection. This mechanism is widely used to explain turn-on signals in similar sensors. However, the photophysical processes of such sensors may be more complex, necessitating a deeper understanding of their underlying sensing mechanisms. This study presents a comprehensive investigation into the photophysical processes and sensing mechanism of a turn-on sensor for Al3+ featuring a Schiff base moiety. Multiple excited-state intramolecular proton transfer (ESIPT) processes are observed, all closely associated with the Schiff base structure. These ESIPT processes trigger CN isomerization, leading to the formation of two nonemissive twisted intramolecular charge transfer (TICT) states. In addition to CN isomerization, two bond rotation processes with lower energy barriers are identified. These rotational processes generate two additional nonemissive TICT states and play a dominant role in the weak fluorescence of the sensor. This elucidation of photophysical processes provides a clearer understanding of the Al3+ sensing mechanism.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500196"},"PeriodicalIF":2.3,"publicationDate":"2025-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144564629","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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Exploring the Reaction Mechanisms and Kinetics of NH₂ Radical with Singlet and Triplet O₂ Molecules: Implications for Modeling Ammonia Oxidation. 探索NH2自由基与单线态和三重态O2分子的反应机理和动力学：模拟氨氧化的意义。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-07-03 DOI: 10.1002/cphc.202500070

Xiaoyang Lei, Tong Si, Bin Yang, Shuiqing Li

{"title":"Exploring the Reaction Mechanisms and Kinetics of NH2 Radical with Singlet and Triplet O2 Molecules: Implications for Modeling Ammonia Oxidation.","authors":"Xiaoyang Lei, Tong Si, Bin Yang, Shuiqing Li","doi":"10.1002/cphc.202500070","DOIUrl":"https://doi.org/10.1002/cphc.202500070","url":null,"abstract":"The detailed mechanism of how the electronically excited species of air plasma promote the combustion of ammonia remains unclear. Herein, the reactions of NH2 radical with both singlet and triplet oxygen molecules are investigated by high-level theoretical calculations. A minimal-energy crossing point is found on the 2A″ and 2A' potential energy surfaces of H2NOO radical, which plays an important role on the product distributions of NH2 + O2(a1Δg) reaction. The temperature- and pressure-dependent rate constants of the reactions are predicted by Rice-Ramsperger-Kassel-Marcus theory and master equation simulations. Subsequently, the influence of O2(a1Δg) on the ignition delay time of ammonia is assessed by updating the existing ammonia combustion model with the computed reaction parameters. The results indicate that 5% O2(a1Δg) in the total oxygen dramatically accelerate the ignition of ammonia by more than one order of magnitude at ≈1000 K and 1 atm, mainly via the NH2 + O2(a1Δg) = H2NO + 3O reaction. Further, the catalytic effects of ammonia, water, and formic acid on the isomerization of the adduct, H2NOO radical, of NH2 + O2 are studied, which will have implications for modeling the oxidation kinetics of ammonia in both atmospheric and combustion conditions.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500070"},"PeriodicalIF":2.3,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144559339","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

Front Cover: Accessing Transient Isomers in the Photoreaction of Metastable-State Photoacid (ChemPhysChem 13/2025) 封面：亚稳态光酸光反应中的瞬态异构体（chemphychem 13/2025）

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-07-03 DOI: 10.1002/cphc.70024

Ying-Zhong Ma, Uvinduni I. Premadasa, May Waters, Nitesh Kumar, Benjamin Doughty, Melyse Laud, Yi Liao, Vyacheslav S. Bryantsev

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Development of Water-Dispersible CuS Nanoparticles for Chemo-Photothermal Therapy and Photoacoustic Application. 用于化学光热和光声治疗的水分散cu纳米颗粒的研制。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-07-03 DOI: 10.1002/cphc.202500016

Sonali Gupta, Bijaideep Dutta, Subhadip Paul, Ratan K Saha, Kanhu C Barick, Puthusserickal A Hassan

{"title":"Development of Water-Dispersible CuS Nanoparticles for Chemo-Photothermal Therapy and Photoacoustic Application.","authors":"Sonali Gupta, Bijaideep Dutta, Subhadip Paul, Ratan K Saha, Kanhu C Barick, Puthusserickal A Hassan","doi":"10.1002/cphc.202500016","DOIUrl":"https://doi.org/10.1002/cphc.202500016","url":null,"abstract":"Photothermal therapy (PTT) is a promising treatment option for cancer. However, biocompatibility, water dispersibility, and good photoresponsiveness are necessary for photothermal agents to be used in PTT. Herein, a soft chemical approach is reported for the design and development of phosphorylethanolamine-functionalized CuS nanoparticles (PEA-CuS NPs) using phosphorylethanolamine (PEA) as a surface passivation agent for combinatorial chemo-photothermal therapy. X-ray diffraction and transmission electron microscopy analyses proved the successful formation of the green covellite CuS phase with an average particle size of 13 nm, while Fourier transform infrared spectroscopy and light scattering measurements demonstrated their surface functionalization with the PEA ligand. The PEA-CuS NPs have exhibited good photothermal heating efficacy upon irradiation of 980 nm laser light. Moreover, the in vitro studies have shown substantial cellular uptake of PEA-CuS NPs in MCF-7 cell lines and their dose-dependent cytotoxicity (83.3 and 65.4% cell-killing efficacy by 100 and 50 μg mL-1 of PEA-CuS NPs, respectively) upon 980 nm laser irradiation (0.65 W power). The developed PEA-CuS NPs have also demonstrated very high acoustic signal under 690 and 530 nm laser light irradiation. Thus, these water-dispersible PEA-CuS NPs can be served as a promising candidate for image-guided combinatorial therapy involving chemotherapy and PTT.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500016"},"PeriodicalIF":2.3,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144559338","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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Cover Feature: Superconducting Lithium Hydride in a Chemical Capacitor Setup: A Theoretical Study (ChemPhysChem 13/2025) 封面特色：超导氢化锂在化学电容器设置：理论研究（chemphysichem 13/2025）

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-07-03 DOI: 10.1002/cphc.70022

Piotr G. Szudlarek, Christopher Renskers, Elena Roxana Margine, Wojciech Grochala

引用次数: 0

Volcano-like Activity Trends in Au@Pd Catalysts: The Role of Pd Loading and Nanoparticle Size. Au@Pd催化剂的火山样活性趋势：Pd负载和纳米颗粒大小的作用。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-07-03 DOI: 10.1002/cphc.202500164

Adriano H Braga, Jhonatan L Fiorio, Ofelia Yang, Karla L C Silva, Tiago A Silva, Adam S Hoffman, Simon R Bare, Jefferson Bettini, Naga Vishnu V Mogili, Liane M Rossi

{"title":"Volcano-like Activity Trends in Au@Pd Catalysts: The Role of Pd Loading and Nanoparticle Size.","authors":"Adriano H Braga, Jhonatan L Fiorio, Ofelia Yang, Karla L C Silva, Tiago A Silva, Adam S Hoffman, Simon R Bare, Jefferson Bettini, Naga Vishnu V Mogili, Liane M Rossi","doi":"10.1002/cphc.202500164","DOIUrl":"https://doi.org/10.1002/cphc.202500164","url":null,"abstract":"The addition of palladium (Pd) to preformed gold nanoparticles (Au NPs) enables the formation of core-shell structures with enhanced catalytic performance in oxidation reactions. However, predicting the precise palladium content required to achieve maximum catalytic activity remains difficult based on current understanding. Herein, Pd was systematically introduced onto titania-supported Au NPs (2, 6, and 10 nm) to evaluate their performance in benzyl alcohol oxidation. A volcano-like trend in catalytic activity was observed, where activity increased with Pd addition, peaked, and then declined. The Pd loading required for maximum activity depended on Au NP size: ≈40 at% Pd/Au for 2.6 nm, ≈20 at% Pd/Au for 6.4 nm, and ≈12.5 at% Pd/Au for 10.6 nm. For Au NPs > 6 nm, peak activity aligned with monolayer Pd coverage, while for smaller NPs (2-3 nm), optimal Pd content was below monolayer predictions. X-ray absorption spectroscopy revealed a core-shell structure at low Pd content, but higher Pd loadings led to Pd diffusion into the Au core. This structural transformation likely caused activity decline, indicating that AuPd alloying negatively impacts catalysis. These results highlight that core-shell Au@Pd catalysts outperform AuPd alloys and provide crucial insights for designing highly active bimetallic catalysts.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500164"},"PeriodicalIF":2.3,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144559340","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

Surface Characterization of N-Heterocyclic Carbenes on Gold and Silver: Exploring Distinct Crystalline Facets. 金和银上n -杂环碳烯的表面表征：探索不同的晶体面。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-07-02 DOI: 10.1002/cphc.202500227

Sayantan Mahapatra, Linfei Li, Nan Jiang

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Structure Formation in the Wetting Layer of a Carbonyl-Functionalized Ionic Liquid on Au(111): How to Control the Functional Group? Au（111）上羰基功能化离子液体润湿层结构的形成：如何控制官能团？

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-07-02 DOI: 10.1002/cphc.202500229

Lukas Knörr, Hanna Bühlmeyer, Julien Steffen, Simon Trzeciak, Jonas Hauner, Dirk Zahn, Andreas Görling, Jörg Libuda

{"title":"Structure Formation in the Wetting Layer of a Carbonyl-Functionalized Ionic Liquid on Au(111): How to Control the Functional Group?","authors":"Lukas Knörr, Hanna Bühlmeyer, Julien Steffen, Simon Trzeciak, Jonas Hauner, Dirk Zahn, Andreas Görling, Jörg Libuda","doi":"10.1002/cphc.202500229","DOIUrl":"https://doi.org/10.1002/cphc.202500229","url":null,"abstract":"Coating heterogeneous catalysts with ionic liquids (ILs), a strategy known as 'solid catalysts with ionic liquid layers', can fine-tune catalytic selectivity. Introducing functional groups into ILs enhances their interaction with reactants, but precise control over their positioning is crucial. The structural formation in the IL wetting layer of the carbonyl-functionalized IL [5-oxo-C6C1Im][NTf2] on Au(111) is investigated using infrared reflection absorption spectroscopy and scanning tunneling microscopy under ultrahigh vacuum conditions, supported by density functional theory and molecular dynamics simulations. At low temperatures (<130 K), the IL forms disordered islands, which coalesce into ordered films near ambient temperature. At low coverage, the IL adopts flat, space-demanding adsorption geometries. Upon forming a closed film, adsorption shifts to more compact configurations, with the carbonyl group tilting toward the vacuum while the ring remains surface-bound. Deposition at 300 K forms crystalline structures in the sub-monolayer regime, where the cation side chain can either stand upright or lie flat depending on the coverage. The IL remains thermally stable and desorbs completely at 500 K without decomposition. These findings highlight how IL coverage and deposition conditions tune functional group orientation at the catalyst interface, optimizing SCILL performance.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500229"},"PeriodicalIF":2.3,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144552470","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

Evidence for Anion-Anion Interaction in Amino Acid Ionic Liquids Probed by Far-Infrared Spectroscopy. 远红外光谱探测氨基酸离子液体中阴离子-阴离子相互作用的证据。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-06-30 DOI: 10.1002/cphc.202500297

David Kotwica, Ralf Ludwig

{"title":"Evidence for Anion-Anion Interaction in Amino Acid Ionic Liquids Probed by Far-Infrared Spectroscopy.","authors":"David Kotwica, Ralf Ludwig","doi":"10.1002/cphc.202500297","DOIUrl":"https://doi.org/10.1002/cphc.202500297","url":null,"abstract":"Herein, it is shown that far-infrared spectroscopy is a sensitive probe for detecting not only cation-anion but also anion-anion interaction in imidazolium-based ionic liquids (ILs). The low-frequency spectra of ILs with the same 1-ethyl-3-methylimidazolium cation but different anions are measured, namely the acetate and glycinate anion, whereby the latter forms the simplest amino acid IL (AAIL). It is shown that two glycinate anions form two hydrogen bonds between either the carboxylate and amino groups allowing for attractive anion-anion interaction despite the Coulomb repulsion between the ions of like charge. The spectral signature of the torsional motion of the amine groups ranges between 200 and 350 cm-1, strongly depending on the binding motif as determined by cation-anion or anion-anion interactions. This is confirmed by density functional theory calculations of frequencies of larger IL clusters exhibiting these characteristic binding motifs. The spectral signatures assigned to the cation-anion interactions are correlated to measured enthalpies of vaporization, confirming a once proposed relation which can be obviously used for predicting thermodynamic properties from spectroscopy for less stable AAILs.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500297"},"PeriodicalIF":2.3,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144526540","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

Accurate and Efficient Description of Acidic Zeolites with Plane-Wave Density Functional Theory Using Range-Separated Hybrid Functionals. 用距离分离杂化泛函的平面波密度泛函理论准确有效地描述酸性沸石。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-06-30 DOI: 10.1002/cphc.202500147

Philipp Huber, Philipp N Plessow

{"title":"Accurate and Efficient Description of Acidic Zeolites with Plane-Wave Density Functional Theory Using Range-Separated Hybrid Functionals.","authors":"Philipp Huber, Philipp N Plessow","doi":"10.1002/cphc.202500147","DOIUrl":"https://doi.org/10.1002/cphc.202500147","url":null,"abstract":"Brønsted acidic zeolites and their reactivity are routinely studied computationally, mainly with periodic density functional theory (DFT) using the generalized gradient approximation (GGA). In many cases, large errors are observed at the GGA-level of theory, in particular reaction barriers are often underestimated and the stability of carbocations is overestimated. The use of ab initio methods, such as MP2 and CCSD(T), also with local approximations, is mostly limited to nonperiodic cluster models. In this work, for a set of reaction energies and barriers, the random phase approximation and common density functionals are investigated by comparison to DLPNO-CCSD(T) and complete basis set extrapolated MP2 calculations on large cluster models. The most accurate functionals are the range-separated hybrids ωB97M-D4, ωB97M-V, ωB97X-D4, ωB97X-V, and ωB97-D. Compared to our reference calculations, these functionals give mean absolute errors below 8 kJ mol-1 and also lead to few outliers. ωB97M-D4 performs best, with an MAE of 5.1 kJ mol-1 and an error that is smaller than that of complete basis set extrapolated MP2. Range-separated functionals are shown to work well in periodic calculations with plane-wave DFT. This allows the efficient calculations of very accurate reaction energies and barriers directly for the periodic system at modest computational cost.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500147"},"PeriodicalIF":2.3,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144526538","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