Dalton Transactions最新文献

{"title":"Bifunctional heterobimetallic 3d-4f [Co(II)-RE, RE = Dy, Eu, Y] ionic complexes: modulation of the magnetic-luminescent behaviour","authors":"Matteo Bombaci, Francesca Lo Presti, Anna Lucia Pellegrino, Martina Lippi, Patrizia Rossi, Leonardo Tacconi, Lorenzo Sorace, Graziella Malandrino","doi":"10.1039/d4dt01693a","DOIUrl":"https://doi.org/10.1039/d4dt01693a","url":null,"abstract":"This work reports the engineering and the functional properties of an emerging class of heterobimetallic 3d-4f ionic complexes designed with cobalt and rare-earth (RE) metals. We present a comprehensive examination of structural, magnetic, optical, and thermal properties of the heterobimetallic ionic complexes with general formula [Co(hfa)<small>₃</small>]-[RE(hfa)<small>₂</small>tetraglyme]+<small></small> (RE = Dy, Eu, Y), where the metal centres are coordinated by the hexafluoroacetylacetonate (Hhfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione), β-diketone and the tetraglyme (2,5,8,11,14-pentaoxapentadecane) polyether. Structural analysis reveals an octahedral coordination geometry enveloping the cobalt(II) centre, characterized by inherent symmetry properties consistent across the derivatives, while a capped square-antiprism coordination polyhedron is observed for the RE ions. Magnetic characterization, employing electron paramagnetic resonance (EPR) spectroscopy, confirms the constancy of the electronic structure of the cobalt(II) moiety and the significant contribution of the lanthanide ions to the magnetic properties of the compounds. The non-trivial single-ion magnetic properties of cobalt(II), dysprosium(III), and europium(III) centres, and the effect of their interactions are investigated by detailed static and dynamic magnetic susceptibility studies. Moreover, optical analyses have been carried out showing the π-π* intraligand (IL) transition of the β-diketonate ligand and the d-d cobalt(II) transitions. Luminescence characterization of dysprosium(III) and europium(III) derivatives exhibits their characteristic emission bands, indicative of the unique photophysical properties conferred by the lanthanide ions. Thermal studies via thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) reveal good thermal stability and volatility properties, underscoring the interesting nature of these ionic complexes. In summary, these heterobimetallic complexes show intriguing optical and magnetic properties with potential implications across diverse scientific disciplines, including molecular magnetism, optoelectronics, and materials science.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556342","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}

{"title":"Quantitative determination and subcellular mapping of Pt-based drugs in single breast tumour cells via Laser Ablation – ICP-Mass Spectrometry","authors":"Legna Colina Vegas, Thibaut Van Acker, Wilmer Villarreal, Olivier De Wever, Alzir A Batista, Joaquim A. Nobrega, Frank Vanhaecke","doi":"10.1039/d4dt02467b","DOIUrl":"https://doi.org/10.1039/d4dt02467b","url":null,"abstract":"For years already, cancer is the second cause of death worldwide, preceded by cardiovascular diseases only. The number of research groups focusing on the discovery of new drugs to treat cancer is growing and the aim is to look for more effective compounds that cause less severe side effects and do not suffer from therapeutic resistance. The metal complexes Cisplatin and Carboplatin are widely used in the chemotherapeutic treatment of various types of cancer, including triple-negative breast cancer (TNBC). Both compounds are essential in modern chemotherapy and continue to be the subject of research to optimize their therapeutic properties and minimize adverse effects. Laser ablation – inductively coupled plasma-mass spectrometry (LA-ICP-MS) allows both quantitative data and information on the spatial distribution of elements in biological tissues and populations of single cells to be obtained. In this work, the content of Pt and its distribution in TNBC MDA-MB-231 cells were determined via LA-ICP-MS analysis after incubation with different Pt-containing drugs. The quantitative analysis of single cells and the elemental maps revealing the distribution of Pt over and within the cells provide an enhanced insight into the potential mechanism of action of these Pt-containing drugs and their efficacy against TNBC.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556344","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}

{"title":"Trigonal Bipyramidal or Square Planar? Density Functional Theory calculations of iron bis(dithiolene) N-heterocyclic carbene complexes","authors":"Katherine Merkel, Alyssa V. B. Santos, Scott Michael Simpson","doi":"10.1039/d4dt02650k","DOIUrl":"https://doi.org/10.1039/d4dt02650k","url":null,"abstract":"Density functional theory (DFT) calculations of 57 iron bis(dithiolene)-N-heterocyclic carbene adducts were conducted to determine what parameters predict, and possibly influence, the coordination of these aforementioned adducts. The parameters considered herein include three different types of nuclear magnetic resonance (C-NMR, Se-NMR, and P-NMR) isotropic chemical shifts, the Tolman Electronic Parameter (TEP), the Huynh Electronic Parameter (HEP), and the percent buried volume (%Vbur) of the different N-heterocyclic carbenes (NHCs) calculated from DFT. These parameters were selected based upon prior literature connection to σ-donor ability, π-acidity, and steric effects. The computed values of the properties were compared via multivariable linear regression models to see which properties best predict the Addison τ parameter—a measure of whether the complex would assume the square pyramidal or trigonal bipyramidal geometry. It was determined that a combination of TEP and %Vbur are the best predictors of the τ value, for the parameters considered herein. The inclusion of additional parameters yields mild improvement to the statistical models for the prediction of the τ value.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142555702","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}

{"title":"The extended investigation of the conductive characteristics of monoclinic tungstates with the Bi3.24Ln2W0.76O10.14 (Ln = La, Pr or Nd) composition","authors":"Ekaterina Orlova, Yelizaveta A. Morkhova, Nikolay Viktorovich Lyskov, Anastasia Egorova, Egor Baldin, Artem A Kabanov, Elena Kharitonova, V. I. Voronkova","doi":"10.1039/d4dt02462a","DOIUrl":"https://doi.org/10.1039/d4dt02462a","url":null,"abstract":"δ-Bi2O3-based materials have long been a focus of interest as potential solid oxide fuel cell materials due to their high electrical conductivity. Here, the extensive studies of thermal stability, polymorphism and conductivity have been carried out for the first time on Bi3.24Ln2W0.76O10.14 (Ln = La, Pr or Nd) compounds in the ternary Bi2O3–Ln2O3–WO3 system, mentioned more than 20 years ago by Watanabe. The obtained single-phase materials were found to be sufficient dense (more than 94%) and thermally stable (up to 900 °C). Emphasis was placed on studying the nature of the electrical transport of these phases, which was investigated through high-throughput calculations and experimental measurements. Theoretical studies included a crystal chemical evaluation of conductivity channels and migration energy, calculation of ionic conductivities using the kinetic Monte Carlo method, and determination of band gaps using a quantum-chemical approach. Experimental conductivity investigations were carried out over a wide temperature range (up to 900 °C) and at various oxygen partial pressures. For Bi3.24Ln2W0.76O10.14, the anionic type of conductivity is predominant with a share of the electronic component. The total conductivity values reached about 10-2 S cm-1 at 900 °C for all samples, confirmed by both calculation and measurement. These theoretical and experimental findings enhance the understanding of the nature and mechanism of Watanabe’s phase conductivity.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142555704","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}

{"title":"The Curious Case of Co-Planarity in Di-nuclear Triel Complexes: A Density Functional Investigation","authors":"Mayank Khera, Neetu Goel","doi":"10.1039/d4dt02453b","DOIUrl":"https://doi.org/10.1039/d4dt02453b","url":null,"abstract":"Density functional investigation of intramolecular triel (Tr) bonding present in di-nuclear aryl complexes of group 13 elements having general formula [(Tr)Me2(2,6- (X)2C6H3O)]2 (Tr = B, Al, Ga, In &amp; Tl and X = OMe, OEt, OH, OPh, NH2, SH, Cl, F) has been performed. Conclusive evidence of the concurrent two σ-hole interaction has been provided by analysis of Tr bond length, interaction energy (∆E), second order perturbation energy (E2), charge transfer (∆q), Quantum theory of atom in molecules (QTAIM) and Noncovalent Interaction (NCI) Plots for 12 complexes. The Tr bond length in the optimized geometry varies from 2.49 to 2.89 Å in Al complexes (1-8) and 2.66 to 2.83 Å in other group 13 element complexes (9-12) at PBE0-D3 functional. The interaction energy calculation reveals that the co-planer structure of complexes containing Al (1-8) are more stable than its rotamer by 8-15 kcal/mol, whereas the di-nuclear complexes of other group 13 (9-12) orient in non-planer pocket structure. This loss of co-planarity reveals the fact that it presence relies on the Tr atom, not the intramolecular Tr bonding, which has a striking impact on the crystal engineering of di-nuclear complexes of Group 13.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556008","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}

{"title":"High-pressure synthesis and crystal structure analysis of PbTeO4, a UV transparent material","authors":"Michael Hladik, Armin Penz, Felix Rainer Serafin Purtscher, Thomas Hofer, Gunter Heymann, Matthias Weil","doi":"10.1039/d4dt02697g","DOIUrl":"https://doi.org/10.1039/d4dt02697g","url":null,"abstract":"Using the additional parameter pressure (Walker-type multianvil device), the lead(II) oxidotellurate(VI) PbTeO<small>₄</small> was synthesized at conditions of 8 GPa and 750 °C, and for the first time its crystal structure was determined using single-crystal X-ray diffraction data. PbTeO<small>₄</small> crystallizes with four formula units in the monoclinic space group <em>I</em>2/<em>a</em> with unit cell parameters <em>a</em> = 5.4142(4), <em>b</em> = 4.9471(4), <em>c</em> = 12.0437(11) Å, <em>β</em> = 99.603(3)°, and V = 318.07(5) Å<small>³</small>. UV-Vis measurements revealed a UV transparency down to 200 nm. From the diffuse reflectance data experimental band gaps (E<small>_g(direct)</small> = 2.9 eV / E<small>_g(indirect)</small> = 2.8 eV) were determined and compared with calculated values. Temperature-dependent X-ray powder diffraction and complementary thermal analysis measurements revealed a stability range of PbTeO<small>₄</small> up to 625 °C. Additionally, theoretical calculations at DFT level of theory were carried out to obtain the electronic band structure, X-ray powder diffraction patterns, IR/Raman vibrational spectra and Mulliken partial charges. The electron localization function (ELF) was visualized to emphasize the presence of the electron lone pair E in the coordination sphere of the Pb<small>^II</small> atom.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556343","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}

{"title":"High-throughput centrifugal evaporation for mesoporous alumina powder synthesis via evaporation-induced self-assembly (EISA)","authors":"Ryutaro Wakabayashi","doi":"10.1039/d4dt02512a","DOIUrl":"https://doi.org/10.1039/d4dt02512a","url":null,"abstract":"The evaporation-induced self-assembly (EISA) process is commonly employed to synthesise mesoporous materials, such as mesoporous alumina. Typically, recovering mesoporous alumina in powder form takes several days due to the need for controlled solvent evaporation conditions. The mesostructure obtained from the EISA process is highly sensitive to these conditions, which can sometimes hinder reproducibility. This paper presents an improved EISA method using a centrifugal evaporator, which enables the rapid recovery of mesoporous alumina powder (approximately 2 h) from multiple precursor solutions under controlled evaporation conditions. The advantages of using a centrifugal evaporator over traditional vacuum evaporation methods include: (1) the reduction of bumping and foaming due to centrifugal force; (2) resistance to evaporated gaseous HCl; and (3) the ability to evaporate multiple samples simultaneously. This enhanced EISA process is expected to accelerate the research progress of powdery mesoporous materials.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142555706","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}

{"title":"Syntheses and Structures of Dimesitylphosphinite Complexes of the Alkali Metals as well as Their Catalytic Activity in Hydro-phosphorylation Reactions","authors":"Benjamin Fener, Philipp Schüler, Phil Liebing, Helmar Görls, Matthias Westerhausen","doi":"10.1039/d4dt02721c","DOIUrl":"https://doi.org/10.1039/d4dt02721c","url":null,"abstract":"Metalation of dimesitylphosphane oxide, Mes<small>₂</small>P(O)H (<strong>1</strong>), with alkali metal reagents (<em>n</em>BuLi, NaH, A(hmds); A = K, Rb, Cs) in THF yields the corresponding dimesitylphosphinites of lithium (<strong>2-thf</strong>), sodium (<strong>3-thf</strong>), potassium (<strong>4-thf</strong>), rubidium (<strong>5-thf</strong>), and caesium (<strong>6</strong>). Their molecular structures exhibit a broad and fascinating variety. The dinuclear compounds <strong>2-thf</strong>, <strong>3-thf</strong>, and <strong>5-thf</strong> have central four-membered A<small>₂</small>O<small>₂</small> rings, whereas the potassium congener crystallises as tetranuclear complex with an inner A<small>₄</small>O<small>₄</small> heterocuban cage. The tetranuclear caesium congener precipitates without thf coligands and exhibits a quite unique structure in its crystalline state. Due to its catalytic activity in hydrophosphorylation reactions, we focus the solvent-structure relationship on the potassium derivatives. In hydrocarbons, [K<small>₄</small>(O-PMes<small>₂</small>)<small>₄</small>]<small>₂</small> (<strong>4</strong>) forms, bidentate Lewis bases like dme and tmeda are unable to deaggregate this tetranuclear cage compound, but bases with a higher denticity (diglyme, triglyme, pmdeta) split this cage compound into dinuclear complexes with central K<small>₂</small>O<small>₂</small> rings. In addition, very bulky P-bound aryl groups like 2,4,6-triisopropylphenyl in dinuclear <strong>8-thf</strong> hinder the formation of tetranuclear cage compounds, whereas 2-methylnaphthyl substituents are not bulky enough and the tetranuclear cage compound <strong>7-thf</strong> forms. For the 2,4,6-triisopropylphenyl substituent, the rubidium and caesium congeners <strong>11 </strong>and <strong>12</strong> crystallise with two central A<small>₂</small>O<small>₂</small> rings interconnected by π-interactions. A heteroleptic potassium complex <strong>9-hmds</strong>, containing hmds as well as phosphinite anions, represents a snapshot on the way from starting K(hmds) to the phosphinite-based heterocubane congener. Finally, heterobimetallic [{(thf)K}<small>₂</small>Mg(O-PMes<small>₂</small>)<small>₄</small>] (<strong>10-thf</strong>) with tetrahedrally coordinated Mg centres has been isolated.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142541130","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}

{"title":"The Mechanism of Mo-Nitrogenase: from N2 capture to first release of NH3","authors":"Ian Dance","doi":"10.1039/d4dt02606c","DOIUrl":"https://doi.org/10.1039/d4dt02606c","url":null,"abstract":"Mo-nitrogenase hydrogenates N<small>₂</small> to NH<small>₃</small>. This report continues from the previous paper [Dalton Transactions 53, 14193 (2024)] that described how the active site FeMo-co of the enzyme is uniquely able to capture and activate N<small>₂</small>, forming a key intermediate with Fe-bound HNNH. Density functional simulations with a 485+ atom model of the active site and surrounds are used to describe here the further reactions of this HNNH intermediate. The first step is hydrogenation to form HNNH<small>₂</small> bridging Fe2 and Fe6. Then a single step reaction breaks the N-N bond, generating an Fe2-NH-Fe6 bridge and forming NH<small>₃</small> bound to Fe6. Then NH<small>₃</small> dissociates from Fe6. Reaction potential energies and kinetic barriers for all steps are reported for the most favourable electronic states of the system. The sequence of steps that follow the Fe2-NH-Fe6 intermediate, forming and dissociating the second NH<small>₃</small>, are outlined, including regeneration of the resting state of the enzyme. These results provide an interpretation of the recent steady-state kinetic data and analysis by Harris et al, [Biochemistry 61, 2131 (2022)] who found a slow step after the formation of the HNNH intermediate. The calculated potential energy barriers for the HNNH<small>₂</small> → NH + NH3 reaction (30 - 36 kcal mol-1), are larger than the potential energy barriers for the N<small>₂</small> → HNNH reaction (19 to 29 kcal mol-1). I propose that the post-HNNH slow step identified kinetically is the key HNNH<small>₂</small> → NH + NH<small>₃</small> reaction described here. This step and the N<small>₂</small>-capture step are the most difficult in the conversion of N<small>₂</small> to 2NH<small>₃</small>. The steps in the complete mechanism still to be computationally detailed are relatively straightforward.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142541131","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}

{"title":"Zn(II) coordination influences the secondary structure, but not antimicrobial activity of the N-terminal histatin 3 hydrolysis product","authors":"Emilia Dzień, Joanna Wątły, Aleksandra Hecel, Aleksandra Mikołajczyk, Agnieszka Matera-Witkiewicz, Miquel Barceló-Oliver, Miquel Adrover, Alicia Dominguez-Martin, Magdalena Rowinska-Zyrek","doi":"10.1039/d4dt02274b","DOIUrl":"https://doi.org/10.1039/d4dt02274b","url":null,"abstract":"The relationship between the coordination chemistry and antimicrobial activity of Zn(II) and Cu(II)-bound histatins, salivary antimicrobial peptides, remains enigmatic. We focus on metal complexes of histatin 3 and its two products of hydrolysis: histatin 4 and its N-terminal fragment (histatin 3-4). The thermodynamic stability of these complexes is quite expected – the binding of Cu(II) via the ATCUN motif results in the formation of very stable complexes. In histatin-Zn(II) complexes, the {2Nim} type of coordination dominates, with polymorphic binding sites observed for histatin 3-4 and 5-8, result in their low thermodynamic stability compared to the complexes of histatin 3, 4, 5 and 8 with Zn(II), in which we observe a {2Nim, O-} type of coordination. Histatin 3, 3-4 and 4 have greater activity against Gram-positive bacteria than against Gram-negative ones, and Cu(II) or Zn(II) binding can, in some cases, moderately increase the antimicrobial activity of the native histatin 3 and 4, but not the remaining 3-4 fragment. The most probable reason for the metal-enhanced antimicrobial activity is, in this case, a local change of charge, while the chemically fascinating metal binding induced structural changes do not result in a change of biological activity. Neither histatin 3-4, the N-terminal fragment of histatin 3, which remains in solution after cleavage, nor its metal complexes have any antimicrobial activity, but histatin 3-4 presents intriguing Zn(II)-induced structural behavior, changing its secondary structure, with a tendency to form an α-helix.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142541128","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}