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Transition-state aromaticity and its relationship with reactivity in pericyclic reactions. 周环反应中过渡态芳构性及其与反应活性的关系。
IF 2.1 4区 化学
Beilstein Journal of Organic Chemistry Pub Date : 2025-08-12 eCollection Date: 2025-01-01 DOI: 10.3762/bjoc.21.125
Israel Fernández
{"title":"Transition-state aromaticity and its relationship with reactivity in pericyclic reactions.","authors":"Israel Fernández","doi":"10.3762/bjoc.21.125","DOIUrl":"10.3762/bjoc.21.125","url":null,"abstract":"<p><p>The influence of transition-state aromaticity on the barrier heights of concerted pericyclic reactions is summarized herein. To this end, selected representative examples ranging from fundamental processes such as Diels-Alder or Alder-ene reactions to double-group transfer reactions or 1,3-dipolar cycloadditions involving metal complexes are presented. It is found that while more synchronous processes tend to exhibit greater aromatic character in their transition states, this increased aromaticity does not necessarily correlate with lower activation barriers. State-of-the-art computational methods on reactivity, such as the combined activation strain model (ASM)-energy decomposition analysis (EDA) method, reveal that factors other than aromaticity govern the barrier heights of these pericyclic reactions.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"21 ","pages":"1613-1626"},"PeriodicalIF":2.1,"publicationDate":"2025-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12362301/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144940723","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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
3-Aryl-2H-azirines as annulation reagents in the Ni(II)-catalyzed synthesis of 1H-benzo[4,5]thieno[3,2-b]pyrroles. Ni（II）催化合成1h -苯并[4,5]噻吩[3,2-b]吡咯中的3-芳基- 2h -氮嘧啶环化试剂
IF 2.1 4区 化学
Beilstein Journal of Organic Chemistry Pub Date : 2025-08-11 eCollection Date: 2025-01-01 DOI: 10.3762/bjoc.21.123
Julia I Pavlenko, Pavel A Sakharov, Anastasiya V Agafonova, Derenik A Isadzhanyan, Alexander F Khlebnikov, Mikhail S Novikov
{"title":"3-Aryl-2<i>H</i>-azirines as annulation reagents in the Ni(II)-catalyzed synthesis of 1<i>H</i>-benzo[4,5]thieno[3,2-<i>b</i>]pyrroles.","authors":"Julia I Pavlenko, Pavel A Sakharov, Anastasiya V Agafonova, Derenik A Isadzhanyan, Alexander F Khlebnikov, Mikhail S Novikov","doi":"10.3762/bjoc.21.123","DOIUrl":"10.3762/bjoc.21.123","url":null,"abstract":"<p><p>A high-yielding method for the synthesis of 3-arylbenzo[4,5]thieno[3,2-<i>b</i>]pyrroles has been developed via pyrrole ring annulation to the aromatic benzo[<i>b</i>]thiophene system, using 3-arylazirines as a N‒C=C synthon. The reaction is catalyzed by Ni(hfacac)<sub>2</sub> and proceeds through the azirine ring opening across the N=C3 bond. Azirines with both electron-donating and electron-withdrawing C3-aryl substituents tolerate the reaction conditions. The reaction of the <i>N</i>-methylindole analog also provides the annulation product but in moderate yield. The described synthesis is the first example of a dealkoxycarbonylative annulation reaction, in which 2<i>H</i>-azirines act as the annulation reagent.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"21 ","pages":"1595-1602"},"PeriodicalIF":2.1,"publicationDate":"2025-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12362299/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144940766","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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 of optically active folded cyclic dimers and trimers. 旋光性折叠环二聚体和三聚体的合成。
IF 2.1 4区 化学
Beilstein Journal of Organic Chemistry Pub Date : 2025-08-11 eCollection Date: 2025-01-01 DOI: 10.3762/bjoc.21.124
Ena Kumamoto, Kana Ogawa, Kazunori Okamoto, Yasuhiro Morisaki
{"title":"Synthesis of optically active folded cyclic dimers and trimers.","authors":"Ena Kumamoto, Kana Ogawa, Kazunori Okamoto, Yasuhiro Morisaki","doi":"10.3762/bjoc.21.124","DOIUrl":"10.3762/bjoc.21.124","url":null,"abstract":"<p><p>Optically active higher-ordered structures, such as one-handed helical and propeller-shaped structures, can be constructed by folding the π-conjugated system using [2.2]paracyclophane as the chiral crossing unit, leading to circularly polarized luminescence (CPL) properties. Chiral cyclic dimers and trimers were synthesized using planar chiral [2.2]paracyclophane-containing enantiopure ribbon-shaped compounds as the chiral monomers. Unicursal π-conjugated systems were folded at the [2.2]paracyclophane units, and exhibited good photoluminescence quantum efficiencies and CPL anisotropy factors. Opposite chiroptical properties were observed between the dimer and trimer, despite the same absolute configuration of the planar chiral [2.2]paracyclophane units, which was reproduced by theoretical studies.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"21 ","pages":"1603-1612"},"PeriodicalIF":2.1,"publicationDate":"2025-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12362300/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144940726","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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
Chemical synthesis of glycan motifs from the antitumor agent PI-88 through an orthogonal one-pot glycosylation strategy. 通过正交一锅糖基化策略合成抗肿瘤药PI-88的糖基序。
IF 2.1 4区 化学
Beilstein Journal of Organic Chemistry Pub Date : 2025-08-06 eCollection Date: 2025-01-01 DOI: 10.3762/bjoc.21.122
Shaokang Yang, Xingchun Sun, Hanyingzi Fan, Guozhi Xiao
{"title":"Chemical synthesis of glycan motifs from the antitumor agent PI-88 through an orthogonal one-pot glycosylation strategy.","authors":"Shaokang Yang, Xingchun Sun, Hanyingzi Fan, Guozhi Xiao","doi":"10.3762/bjoc.21.122","DOIUrl":"10.3762/bjoc.21.122","url":null,"abstract":"<p><p>Chemical synthesis of monophosphorylated glycan motifs from the antitumor agent PI-88 has been achieved through an orthogonal one-pot glycosylation strategy on the basis of glycosyl <i>ortho</i>-(1-phenylvinyl)benzoates, which not only accelerated synthesis, but also precluded the potential issues inherent to one-pot glycan assembly associated with thioglycosides. The following aspects were featured in synthetic approaches: 1) synthesis of trisaccharide and tetrasaccharide PI-88 glycans via [1 + 1 + 1] and [1 + 1 + 1 + 1] one-pot orthogonal glycosylation, respectively; 2) synthesis of PI-88 glycan motif pentasaccharide via [1 + 1 + 1] and [1 + 1 + 3] one-pot orthogonal glycosylation; 3) synthesis of hexasaccharide via [1 + 1 + 1] and [1 + 1 + 1 + 3] one-pot assembly.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"21 ","pages":"1587-1594"},"PeriodicalIF":2.1,"publicationDate":"2025-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12337991/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144820460","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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
Thermodynamic equilibrium between locally excited and charge transfer states in perylene-phenothiazine dyads. 苝-吩噻嗪二元化合物中局部激发态和电荷转移态的热力学平衡。
IF 2.1 4区 化学
Beilstein Journal of Organic Chemistry Pub Date : 2025-08-05 eCollection Date: 2025-01-01 DOI: 10.3762/bjoc.21.121
Issei Fukunaga, Shunsuke Kobashi, Yuki Nagai, Hiroki Horita, Hiromitsu Maeda, Yoichi Kobayashi
{"title":"Thermodynamic equilibrium between locally excited and charge transfer states in perylene-phenothiazine dyads.","authors":"Issei Fukunaga, Shunsuke Kobashi, Yuki Nagai, Hiroki Horita, Hiromitsu Maeda, Yoichi Kobayashi","doi":"10.3762/bjoc.21.121","DOIUrl":"10.3762/bjoc.21.121","url":null,"abstract":"<p><p>We report the excited-state dynamics of π-orthogonal donor-acceptor dyads based on perylene (Pe) and phenothiazine (PTZ), in which triphenylamine (TPA) units and a phenyl spacer were introduced to modulate donor strength and spatial separation. Among the series, Pe-PTZ(TPA)<sub>2</sub> exhibits a distinct thermal equilibrium between the locally excited (LE) state of the PTZ moiety and the photoinduced charge-transfer (CT) state. Femtosecond to microsecond transient absorption spectroscopy reveals that this equilibrium is facilitated not simply by enhanced donor ability, but presumably by excited-state planarization of the PTZ moiety, which lowers the energy of the LE state of the PTZ moiety. In contrast, Pe-Ph-PTZ(TPA)<sub>2</sub>, in which the donor-acceptor distance is increased by a phenyl spacer, does not show clear equilibrium behavior. These results underscore the crucial role of excited-state structural relaxation in tuning photoinduced charge separation, and demonstrate that precise electronic and geometric design can enable controllable excited-state behavior in orthogonal molecular systems.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"21 ","pages":"1577-1586"},"PeriodicalIF":2.1,"publicationDate":"2025-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12337995/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144820462","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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
pH-Controlled isomerization kinetics of ortho-disubstituted benzamidines: E/Z isomerism and axial chirality. 邻二取代苯并脒的ph控制异构化动力学：E/Z异构和轴向手性。
IF 2.1 4区 化学
Beilstein Journal of Organic Chemistry Pub Date : 2025-08-04 eCollection Date: 2025-01-01 DOI: 10.3762/bjoc.21.120
Ryota Kimura, Satoshi Ichikawa, Akira Katsuyama
{"title":"pH-Controlled isomerization kinetics of <i>ortho</i>-disubstituted benzamidines: <i>E</i>/<i>Z</i> isomerism and axial chirality.","authors":"Ryota Kimura, Satoshi Ichikawa, Akira Katsuyama","doi":"10.3762/bjoc.21.120","DOIUrl":"10.3762/bjoc.21.120","url":null,"abstract":"<p><p>pH-Responsive molecular switches and motors are a class of organic molecules whose three-dimensional structure can be changed by acid-base stimuli. To date, pH-responsive molecular switches have been developed using various functional groups, but further advances require expanding the range of pH-responsive systems and discovering new molecular architectures. Here, we investigate the pH-responsive behavior of <i>ortho</i>-disubstituted benzamidine, which generates atropisomers and <i>E</i>/<i>Z</i> isomers. The amidine moiety allows modulation of the C-N and C-N/C-C rotational barriers by protonation, providing a novel approach to control the kinetics of isomerization via pH adjustment. The results showed that protonation of the amidine moiety significantly suppresses both C-N bond rotation and C-N/C-C concerted rotation, demonstrating the potential of <i>ortho</i>-disubstituted benzamidine derivatives as a novel pH-responsive molecular switch.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"21 ","pages":"1568-1576"},"PeriodicalIF":2.1,"publicationDate":"2025-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12337994/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144820461","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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
Facile synthesis of hydantoin/1,2,4-oxadiazoline spiro-compounds via 1,3-dipolar cycloaddition of nitrile oxides to 5-iminohydantoins. 1,3-偶极环加成法合成邻苯二甲酸乙酯/1,2,4-恶二唑啉螺环化合物。
IF 2.1 4区 化学
Beilstein Journal of Organic Chemistry Pub Date : 2025-07-31 eCollection Date: 2025-01-01 DOI: 10.3762/bjoc.21.118
Juliana V Petrova, Varvara T Tkachenko, Victor A Tafeenko, Anna S Pestretsova, Vadim S Pokrovsky, Maxim E Kukushkin, Elena K Beloglazkina
{"title":"Facile synthesis of hydantoin/1,2,4-oxadiazoline spiro-compounds via 1,3-dipolar cycloaddition of nitrile oxides to 5-iminohydantoins.","authors":"Juliana V Petrova, Varvara T Tkachenko, Victor A Tafeenko, Anna S Pestretsova, Vadim S Pokrovsky, Maxim E Kukushkin, Elena K Beloglazkina","doi":"10.3762/bjoc.21.118","DOIUrl":"10.3762/bjoc.21.118","url":null,"abstract":"<p><p>The cycloaddition of 1,3-dipoles at C=N bonds is a relatively rare process, in contrast to the widespread cycloaddition reactions at C=C, C≡C, and C=S bonds. In this study, we present the syntheses of novel hydantoin/1,2,4-oxadiazoline spiro-compounds using a 1,3-dipolar cycloaddition of nitrile oxides to C=N bonds of 5-iminohydantoins. The efficiency of the approach was demonstrated by varying the substituents at four positions of the resulting spirocyclic molecules. Cytotoxicity of the target hydantoin/1,2,4-oxadiazolines was shown to exceed previously known spiro-compounds bearing only hydantoins or 1,2,4-oxadiazolines (IC<sub>50</sub> values were 30-50 μM, HCT116 cell lines).</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"21 ","pages":"1552-1560"},"PeriodicalIF":2.1,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12320734/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144783376","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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 of an aza[5]helicene-incorporated macrocyclic heteroarene via oxidation of an o-phenylene-pyrrole-thiophene icosamer. 通过氧化邻苯-吡咯-噻吩二聚体合成含杂环螺旋烯的大环杂芳烃。
IF 2.1 4区 化学
Beilstein Journal of Organic Chemistry Pub Date : 2025-07-31 eCollection Date: 2025-01-01 DOI: 10.3762/bjoc.21.119
Yusuke Matsuo, Aoi Nakagawa, Shu Seki, Takayuki Tanaka
{"title":"Synthesis of an aza[5]helicene-incorporated macrocyclic heteroarene via oxidation of an <i>o</i>-phenylene-pyrrole-thiophene icosamer.","authors":"Yusuke Matsuo, Aoi Nakagawa, Shu Seki, Takayuki Tanaka","doi":"10.3762/bjoc.21.119","DOIUrl":"10.3762/bjoc.21.119","url":null,"abstract":"<p><p>The intramolecular oxidative fusion reaction of macrocyclic heteroaromatic arrays has provided strained polycyclic heteroaromatic macrocycles as promising functional molecules. In this study, we prepared an <i>ortho</i>-phenylene-pyrrole-thiophene hybrid icosamer, as the largest cyclic array in the series. The oxidative fusion reaction with [bis(trifluoroacetoxy)iodo]benzene (PIFA) afforded a cyclophane-type aza[5]helicene-incorporated macrocycle, the structure of which was unambiguously revealed by X-ray diffraction analysis. Its optical properties have been investigated in detail.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"21 ","pages":"1561-1567"},"PeriodicalIF":2.1,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12320735/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144783388","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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
Azide-alkyne cycloaddition (click) reaction in biomass-derived solvent CyreneTM under one-pot conditions. 叠氮化物-炔环加成反应（点击）在生物质衍生溶剂CyreneTM中一锅条件下。
IF 2.1 4区 化学
Beilstein Journal of Organic Chemistry Pub Date : 2025-07-30 eCollection Date: 2025-01-01 DOI: 10.3762/bjoc.21.117
Zoltán Medgyesi, László T Mika
{"title":"Azide-alkyne cycloaddition (click) reaction in biomass-derived solvent Cyrene<sup>TM</sup> under one-pot conditions.","authors":"Zoltán Medgyesi, László T Mika","doi":"10.3762/bjoc.21.117","DOIUrl":"10.3762/bjoc.21.117","url":null,"abstract":"<p><p>It was demonstrated that Cyrene<sup>TM</sup>, as a biomass-originated polar aprotic solvent, could be utilized as an alternative reaction medium for one-pot copper(I)-catalyzed azide-alkyne cycloaddition (click or CuAAC) reactions, for the synthesis of various 1,2,3-triazoles under mild conditions. Nineteen products involving <i>N</i>-substituted-4-phenyl-1<i>H</i>-1,2,3- and 1-allyl-4-substituted-1<i>H</i>-1,2,3-triazoles were synthesized under one-pot conditions and isolated with good to excellent yields (50-96%) and purity (>98%). The observed results represent an example that proves that biomass-derived safer solvents can be introduced into a synthetically important transformation exhibiting higher chemical and environmental safety.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"21 ","pages":"1544-1551"},"PeriodicalIF":2.1,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12320739/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144783373","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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
General method for the synthesis of enaminones via photocatalysis. 光催化合成胺酮的一般方法。
IF 2.1 4区 化学
Beilstein Journal of Organic Chemistry Pub Date : 2025-07-29 eCollection Date: 2025-01-01 DOI: 10.3762/bjoc.21.116
Paula Pérez-Ramos, Raquel G Soengas, Humberto Rodríguez-Solla
{"title":"General method for the synthesis of enaminones via photocatalysis.","authors":"Paula Pérez-Ramos, Raquel G Soengas, Humberto Rodríguez-Solla","doi":"10.3762/bjoc.21.116","DOIUrl":"10.3762/bjoc.21.116","url":null,"abstract":"<p><p>Enaminones are key intermediates in the synthesis of several derivatives with important applications in medicinal chemistry. Furthermore, many marketed drugs feature the enaminone structural moiety. In this context, we have developed a photoredox and nickel catalytic system to rapidly forge the enaminone scaffold from 3-bromochromones via a Michael reaction of an amine with an electron-deficient alkene moiety and subsequent photocatalyzed debromination. With this dual catalytic system, a range of structurally diverse enaminone derivatives have been achieved in good yields with total <i>trans</i> selectivity. Mechanistic studies indicate that the key to the success of this process is the formation of an unexplored ternary Ni-complex with 3-bromochromone and a pyridinium salt, which is crucial for the effective activation of the α,β-unsaturated system towards the nucleophilic addition.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"21 ","pages":"1535-1543"},"PeriodicalIF":2.1,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12320736/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144783387","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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
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