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Probing the Local Polarity in Biocompatible Nanocarriers with Solvatofluorochromism of a 4-Carbazole-1,8-naphthalimide Dye 用4-咔唑-1,8-萘酰亚胺染料的溶剂荧光性探测生物相容性纳米载体的局部极性
Photochem Pub Date : 2022-06-24 DOI: 10.3390/photochem2030034
Ana M. Diniz, R. Cruz, J. Avó
{"title":"Probing the Local Polarity in Biocompatible Nanocarriers with Solvatofluorochromism of a 4-Carbazole-1,8-naphthalimide Dye","authors":"Ana M. Diniz, R. Cruz, J. Avó","doi":"10.3390/photochem2030034","DOIUrl":"https://doi.org/10.3390/photochem2030034","url":null,"abstract":"The study of local polarity at the nanoscale is of crucial importance for the development of smart drug delivery systems and photonic materials and is frequently accomplished with the use of luminescent tracer dyes. Nile Red is often used for this purpose, owing to its polarity-sensitive internal charge transfer transition, but its performance is affected by specific solute-solvent interactions that prevent its widespread applicability. Herein, we develop a new 1,8-naphthalimide dye with a strong charge-transfer transition that results in a large dipole moment change upon excitation. This leads to luminescence properties with high sensitivity to solvent polarity, that are independent of specific or inductive interactions. These properties are explored to probe the polarity of biocompatible nanocarriers. This dye was effective in probing the properties of polymeric nanoparticles, allowing the accurate calculation of polarity descriptors and dielectric constants.","PeriodicalId":74440,"journal":{"name":"Photochem","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"44259338","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 2
Antibacterial Activity of In Situ Generated Silver Nanoparticles in Hybrid Silica Films 原位生成的纳米银在杂化二氧化硅膜中的抗菌活性
Photochem Pub Date : 2022-06-23 DOI: 10.3390/photochem2030033
S. Pal, R. Nisi, A. Licciulli
{"title":"Antibacterial Activity of In Situ Generated Silver Nanoparticles in Hybrid Silica Films","authors":"S. Pal, R. Nisi, A. Licciulli","doi":"10.3390/photochem2030033","DOIUrl":"https://doi.org/10.3390/photochem2030033","url":null,"abstract":"Herein we present silver nanoparticles (AgNPs)-doped inorganic–organic hybrid silica films on glass and polypropylene substrates. A hybrid inorganic–organic silica sol in alcoholic medium was prepared at room temperature using TEOS, GLYMO, and APTES. Silver nanoparticles were generated in situ within the hybrid silica sol. AgNPs-SiO2 film was obtained by dip coating method following drying at 80 °C. FTIR spectra shows several vibrational bands of the hybrid silica network and amine functionalization. AgNPs formation was observed from the XRD spectra of the dried film. UV–Visible spectra show sharp surface plasmon resonance (SPR) band centered at 412 nm arising from the evenly distributed silver nanoparticle inside the silica film that was supported by morphological characterization. Both the coated films showed good antibacterial activity against E. coli bacterial strain by forming a zone of inhibition in the agar diffusion test. The antibacterial efficiency for coated glass and polypropylene was 72.5% and 83.75%. This coating approach provides a straight-forward solution to prepare antibacterial coatings on various substrates especially on plastics, where low temperature processing is necessary.","PeriodicalId":74440,"journal":{"name":"Photochem","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42698673","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 3
UPS, XPS, NEXAFS and Computational Investigation of Acrylamide Monomer UPS、XPS、NEXAFS及丙烯酰胺单体的计算研究
Photochem Pub Date : 2022-06-22 DOI: 10.3390/photochem2030032
L. Evangelisti, S. Melandri, F. Negri, M. Coreno, K. Prince, A. Maris
{"title":"UPS, XPS, NEXAFS and Computational Investigation of Acrylamide Monomer","authors":"L. Evangelisti, S. Melandri, F. Negri, M. Coreno, K. Prince, A. Maris","doi":"10.3390/photochem2030032","DOIUrl":"https://doi.org/10.3390/photochem2030032","url":null,"abstract":"Acrylamide is a small conjugated organic compound widely used in industrial processes and agriculture, generally in the form of a polymer. It can also be formed from food and tobacco as a result of Maillard reaction from reducing sugars and asparagine during heat treatment. Due to its toxicity and possible carcinogenicity, there is a risk in its release into the environment or human intake. In order to provide molecular and energetic information, we use synchrotron radiation to record the UV and X-ray photoelectron and photoabsorption spectra of acrylamide. The data are rationalized with the support of density functional theory and ab initio calculations, providing precise assignment of the observed features.","PeriodicalId":74440,"journal":{"name":"Photochem","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-06-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41521680","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 3
Phototransformations of 2,3-Diamino-2-Butenedinitrile (DAMN) Monomers Isolated in Low-Temperature Argon Matrix 低温氩气基质中分离的2,3-二氨基-2-丁腈(DAMN)单体的光转化
Photochem Pub Date : 2022-06-16 DOI: 10.3390/photochem2020031
I. Reva, H. Rostkowska, L. Lapinski
{"title":"Phototransformations of 2,3-Diamino-2-Butenedinitrile (DAMN) Monomers Isolated in Low-Temperature Argon Matrix","authors":"I. Reva, H. Rostkowska, L. Lapinski","doi":"10.3390/photochem2020031","DOIUrl":"https://doi.org/10.3390/photochem2020031","url":null,"abstract":"UV-induced transformations were studied for monomers of 2,3-diamino-2-butenedinitrile (DAMN) isolated in argon matrices. Photoinduced hydrogen-atom transfer was found to be the major process occurring upon UV (λ > 320 nm or λ > 295 nm) excitation of matrix-isolated DAMN monomers. As a result of the transfer of a hydrogen atom from an amino group to a nitrile fragment, a tautomer of DAMN involving a ketenimine group was generated. Identification of this photo-produced species was based on comparison of its experimental IR spectrum with the spectrum theoretically predicted for the ketenimine form. Another product photogenerated upon UV (λ > 320 nm, λ > 295 nm, or λ > 270 nm) irradiation of DAMN isolated in Ar matrices was identified as 4-amino-1H-imidazole-5-carbonitrile (AICN). The structure of this photoproduct was unambiguously assigned on the basis of an exact match of wavenumbers of the bands in the IR spectrum of this photogenerated species and the wavenumbers of IR bands of AICN trapped (in a separate experiment) from the gas phase into an Ar matrix.","PeriodicalId":74440,"journal":{"name":"Photochem","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47559871","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
UV-Vis Spectrophotometer as an Alternative Technique for the Determination of Hydroquinone in Vinyl Acetate Monomer 紫外-可见分光光度法测定醋酸乙烯单体中对苯二酚
Photochem Pub Date : 2022-06-15 DOI: 10.3390/photochem2020030
Md Al Mamunur Rashid, Mofizur Rahman, A. Mahmud, A. Morshed, M. Haque, M. Hossain
{"title":"UV-Vis Spectrophotometer as an Alternative Technique for the Determination of Hydroquinone in Vinyl Acetate Monomer","authors":"Md Al Mamunur Rashid, Mofizur Rahman, A. Mahmud, A. Morshed, M. Haque, M. Hossain","doi":"10.3390/photochem2020030","DOIUrl":"https://doi.org/10.3390/photochem2020030","url":null,"abstract":"As an appropriate quantity of hydroquinone (HQ) is essential to safeguard inhibition characteristics by eliminating the risk of self-polymerization of vinyl acetate monomer (VAM), the determination of the HQ content in VAM is very crucial to ensure the stability of VAM during storage and transportation as well as to achieve the possibility of a proper polymerization reaction. In this study, a simple, cheap, time-saving, and easy method has been developed by which the HQ content in VAM can be measured quickly based on the measurement of UV-Vis absorbance of the HQ content at 293 nm using methanol as a blank. No color development is required for this determination process, and the HQ content in the VAM can be measured directly without any further processing. The limit of detection, limit of quantification, linearity range, accuracy, precision, robustness, and measurement uncertainty of this method have been measured and analyzed and found to be within the acceptable limit and range. The method shows linearity within 0.36–25.0 ppm HQ content in the solution range with a regression coefficient of 0.9999, a relative spike recovery of 101.35%, precision of 1.36%, relative bias of 0.55%, and robustness with a temperature variation of −5 °C.","PeriodicalId":74440,"journal":{"name":"Photochem","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-06-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42290976","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 3
Fluorescence and Phosphorescence of Flavylium Cation Analogues of Anthocyanins 花青素黄离子类似物的荧光和磷光
Photochem Pub Date : 2022-06-08 DOI: 10.3390/photochem2020029
G. T. Silva, Cássio A. P. Silva, Karen M. Silva, R. Pioli, T. S. Costa, Vinícius V. Marto, A. Freitas, Jennifer Rozendo, Lucas M. O. S. Martins, Victor F. Cavalcante, Liuqing Sun, A. Aquino, Vânia M. T. Carneiro, F. Quina
{"title":"Fluorescence and Phosphorescence of Flavylium Cation Analogues of Anthocyanins","authors":"G. T. Silva, Cássio A. P. Silva, Karen M. Silva, R. Pioli, T. S. Costa, Vinícius V. Marto, A. Freitas, Jennifer Rozendo, Lucas M. O. S. Martins, Victor F. Cavalcante, Liuqing Sun, A. Aquino, Vânia M. T. Carneiro, F. Quina","doi":"10.3390/photochem2020029","DOIUrl":"https://doi.org/10.3390/photochem2020029","url":null,"abstract":"Fluorescence spectra and lifetimes were determined for 16 synthetic flavylium cation analogues of anthocyanin plant pigments in dry acetonitrile acidified with trifluoroacetic acid (TFA). Phosphorescence was also observed from the lowest excited triplet state for all of the flavylium cations at 77 K in a rigid TFA-acidified isopropanol glass. The fluorescence quantum yields and lifetimes depend in a systematic manner on the nature and position of the substituents on the flavylium chromophore and three specific substitution patterns associated with significant decreases in the fluorescence quantum yield were identified. A 4′-bromo or 4′-iodo substituent in the B-ring of the flavylium cation produced a small but normal heavy-atom effect, reducing the fluorescence quantum yield and the phosphorescence lifetime relative to analogues without the halogen atom. In contrast, three flavylium cations with a 3′-bromo substituent exhibited an “inverse” heavy atom effect, i.e., an increase in the fluorescence quantum yield rather than a decrease, which was rationalized on the basis of the nodal properties of the natural transition orbitals (NTOs) involved in the S0→S1 radiative transition.","PeriodicalId":74440,"journal":{"name":"Photochem","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-06-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"44760690","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 3
Conformational Structure, Infrared Spectra and Light-Induced Transformations of Thymol Isolated in Noble Gas Cryomatrices 稀有气体低温基质中胸腺嘧啶的构象结构、红外光谱和光诱导转化
Photochem Pub Date : 2022-06-07 DOI: 10.3390/photochem2020028
A. Lopes Jesus, Cláudio M. Nunes, I. Reva
{"title":"Conformational Structure, Infrared Spectra and Light-Induced Transformations of Thymol Isolated in Noble Gas Cryomatrices","authors":"A. Lopes Jesus, Cláudio M. Nunes, I. Reva","doi":"10.3390/photochem2020028","DOIUrl":"https://doi.org/10.3390/photochem2020028","url":null,"abstract":"The conformational space of the natural product thymol (2-isopropyl-5-methylphenol) was investigated using quantum chemical calculations at the B3LYP and MP2 levels, which revealed the existence of four types of conformers differing in the orientation of the isopropyl and hydroxyl groups. Thymol monomers were isolated in noble gas (Ar and Xe) matrices (at 15 K) and characterized by IR spectroscopy. With the support of B3LYP harmonic vibrational calculations, the two most stable trans-OH-conformers, differing in the isopropyl orientation, were identified in the cryomatrices. The two less stable cis-OH conformers were not detected as they shall undergo fast tunneling to the most stable ones. Annealing experiments in a Xe matrix up to 75 K did not lead to any conversion between the two isolated conformers, which is in accordance with the significative energy barrier computed for rotamerization of the bulky isopropyl group (~24 kJ mol−1). Vibrational excitation promoted by broadband or by narrowband irradiation, at the 2ν(OH) frequencies of the isolated conformers, did not lead to any conversion either, which was interpreted in terms of a more efficient energy transfer to the hydroxyl rotamerization (associated with a lower energy barrier and a light H-atom) than to the isopropyl rotamerization coordinate. Broadband UV irradiation experiments (λ > 200 nm) led to a prompt transformation of matrix isolated thymol, with spectroscopic evidence suggesting the formation of isomeric alkyl-substituted cyclohexadienones, Dewar isomers and open-chain conjugated ketenes. The photochemical mechanism interpretation concords with that reported for analogous phenol derivatives.","PeriodicalId":74440,"journal":{"name":"Photochem","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48500104","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 2
Photochemistry of Metal Nitroprussides: State-of-the-Art and Perspectives 金属硝基苯的光化学:现状和展望
Photochem Pub Date : 2022-05-31 DOI: 10.3390/photochem2020027
P. M. Crespo, O. F. Odio, E. Reguera
{"title":"Photochemistry of Metal Nitroprussides: State-of-the-Art and Perspectives","authors":"P. M. Crespo, O. F. Odio, E. Reguera","doi":"10.3390/photochem2020027","DOIUrl":"https://doi.org/10.3390/photochem2020027","url":null,"abstract":"This contribution summarizes the current state in the photochemistry of metal nitroprussides, which is dominated by the electronic structure of the nitrosyl group. From the combination of p orbitals of the nitrogen and oxygen atoms in the NO+ ligand, a π*NO molecular orbital of relatively low energy is formed, which has π*2px and π*2py character. This is a double degenerate orbital. When the nitrosyl group is found coordinated to the iron atom in the nitroprusside ion, the availability of that low energy π*NO orbital results in light-induced electronic transitions from the iron atom dxy, dxz and dyz orbitals, 2b2 (xy) → 7e (π*NO) and 6e (xz,yz) → 7e (π*NO), which are observed at 498 and 394 nm, respectively. These light-induced transitions and the possibility of NO isomer formation dominate the photochemistry of metal nitroprussides. In this feature paper, we discuss the implications of such transitions in the stability of coordination compounds based on the nitroprusside ion in the presence of water molecules for both 3D and 2D structures, including the involved degradation mechanisms. These photo-induced electronic transitions modify the physical and functional properties of solids where the nitroprusside ion forms part of their structure and appear as an opportunity for tuning their magnetic, electrical, optical and as energy-applied materials, for instance. This contribution illustrates these opportunities with results from some recently reported studies, and possible research subjects, even some not explored, are mentioned.","PeriodicalId":74440,"journal":{"name":"Photochem","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49159353","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 1
UV-Induced Benzyloxy Rotamerization in an Ortho OH-Substituted Aryl Schiff Base 紫外光诱导邻羟基取代芳基席夫碱的苯氧基旋转聚合
Photochem Pub Date : 2022-05-25 DOI: 10.3390/photochem2020026
İ. Sıdır, Y. Gülseven Sıdır, Sándor Góbi, H. Berber, R. Fausto
{"title":"UV-Induced Benzyloxy Rotamerization in an Ortho OH-Substituted Aryl Schiff Base","authors":"İ. Sıdır, Y. Gülseven Sıdır, Sándor Góbi, H. Berber, R. Fausto","doi":"10.3390/photochem2020026","DOIUrl":"https://doi.org/10.3390/photochem2020026","url":null,"abstract":"A new benzyloxy containing ortho hydroxyl-substituted aryl Schiff base, trans 2-((2-(benzyloxy)benzylidene) amino)phenol (abbreviated as BBAP), was synthesized and characterized by 1H-, 13C-NMR and infrared spectroscopic techniques and elemental analysis. The conformational landscape of the compound, as well as its infrared spectra in argon and N2 cryogenic matrices (10 K) were investigated, followed by the study of the effects of in situ UV irradiation of the matrix-isolated compound. The structural information was obtained through an extensive series of quantum chemical calculations performed at the DFT(B3LYP)/6-311++G(d,p) level of theory, which enabled to identify 3 low-energy OH···N intramolecularly H-bonded conformers of the molecule that were later found to be present in the as-deposited cryogenic matrices. The 3 experimentally relevant conformers of BBAP differ in the geometry of the benzyloxy substituent, and were discovered to interconvert upon in situ UV irradiation (λ = 230 nm) of the matrix-isolated compound. This is the first report on UV-induced conformational changes taking place in a benzyloxy fragment for a matrix-isolated compound.","PeriodicalId":74440,"journal":{"name":"Photochem","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48378032","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Electronic Absorption, Emission, and Two-Photon Absorption Properties of Some Extended 2,4,6-Triphenyl-1,3,5-Triazines 一些扩展2,4,6-三苯基-1,3,5-三嗪类化合物的电子吸收、发射和双光子吸收特性
Photochem Pub Date : 2022-05-19 DOI: 10.3390/photochem2020023
Alison G. Barnes, N. Richy, Anissa Amar, M. Blanchard‐Desce, A. Boucekkine, O. Mongin, F. Paul
{"title":"Electronic Absorption, Emission, and Two-Photon Absorption Properties of Some Extended 2,4,6-Triphenyl-1,3,5-Triazines","authors":"Alison G. Barnes, N. Richy, Anissa Amar, M. Blanchard‐Desce, A. Boucekkine, O. Mongin, F. Paul","doi":"10.3390/photochem2020023","DOIUrl":"https://doi.org/10.3390/photochem2020023","url":null,"abstract":"We report herein the linear optical properties of some extended 2,4,6-triphenyl-s-triazines of formula 2,4,6-[(1,4-C6H4)C≡C(4-C6H4X)]3-1,3,5-(C3H3N3) (3-X; X = NO2, CN, OMe, NMe2, NPh2) and related analogues 4 and 7-X (X = H, NPh2), before briefly discussing their two-photon absorption (2PA) cross-sections. Their 2PA performance is discussed in relation to 2PA values previously measured for closely related octupoles such as N,N′,N″-triphenylisocyanurates (1-X, 5, and 6-X) or 1,3,5-triphenylbenzenes (2-X). While s-triazines are usually much better two-photon absorbers in the near-IR range than these molecules, especially when functionalised by electron-releasing substituents at their periphery, they present a decreased transparency window in the visible range due to their red-shifted first 1PA peak, in particular when compared with corresponding isocyanurates analogues. In contrast, due to their significantly larger two-photon brilliancy, 2,4,6-triphenyl-s-triazines appear more promising than the latter for two-photon fluorescence bio-imaging purposes. Rationalisation of these unexpected outcomes is proposed based on DFT calculations.","PeriodicalId":74440,"journal":{"name":"Photochem","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46589554","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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