JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
·
2014
·
IF 3.679
Sheng-Jie Chen,Yong-Qi Li,Yong-Yong Wang,Xiao-Li Zhao,Ye Liu
The ionic hybrid P,N-ligands of 1 and 2 have been synthesized as one type of unconventional tertiary phosphines with the advantages of both the π-accepting ligands and the hemilabile ligands. The corresponding ionic Rh(I)-complexes of 1A and 2A proved to be more efficient catalysts for hydroformylation of 1-octene over isomerization than the traditional Rh I (acac)(CO)(PPh 3 ), due to the π-backdonation interaction in Rh → P linkage and the hemilabile ligation of N,P-coordinating sites to Rh-center. The in situ high-pressure FT-IR analysis indicated that: (1) the formation and lifetime of the active Rh H species (2047 cm −1 ) derived from 1A are facilitated by the presence of ligand 1 ; (2) the formation of the active Rh H species is depressed without the aid of the P,N-hemilabile ligation; and (3) the active Rh H species derived from Rh I (acac)(CO)(PPh 3 ) is unstable and susceptible to the formation of the inactive carbonyl-bridged Rh-dimer.
研究领域:
化学
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催化反应
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DOI
高影响因子
Catalysts
·
2019
·Vol. 10
·期 1
·10
·
IF 3.444
Wan-Qiang Wang,Hua Cheng,Ye Yuan,Yu-Qing He,Hua-Jing Wang,Zhi-Qin Wang,Wei Sang,Cheng Chen,Francis Verpoort
The transition-metal-catalyzed alcohol dehydrogenation to carboxylic acids has been identified as an atom-economical and attractive process. Among various catalytic systems, Ru-based systems have been the most accessed and investigated ones. With our growing interest in the discovery of new Ru catalysts comprisingN-heterocyclic carbene (NHC) ligands for the dehydrogenative reactions of alcohols, we designed and prepared five NHC/Ru complexes ([Ru]-1–[Ru]-5) bearing different ancillary NHC ligands. Moreover, the effects of ancillary and additional ligands on the alcohol dehydrogenation with KOH were thoroughly explored, followed by the screening of other parameters. Accordingly, a highly active catalytic system, which is composed of[Ru]-5combined with an additional NHC precursorL5, was discovered, affording a variety of acid products in a highly efficient manner. Gratifyingly, an extremely low Ru loading (125 ppm) and the maximum TOF value until now (4800) were obtained.Keywords:ruthenium (Ru);N-heterocyclic carbenes (NHCs);carboxylic acids;ancillary ligands;additional ligands
研究领域:
化学
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催化反应
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DOI
高影响因子
Nature Communications
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2022
·Vol. 13
·期 1
·1-7
·
IF 17.694
Song Yongbo,Li Yingwei,Zhou Meng,Li Hao,Xu Tingting,Zhou Chuanjun,Ke Feng,Huo Dayujia,Wan Yan,Jie Jialong,Xu Wen Wu,Zhu Manzhou,Jin Rongchao
The growth of nanoparticles along one or two directions leads to anisotropic nanoparticles, but the nucleation (i.e., the formation of small seeds of specific shape) has long been elusive. Here, we show the total structure of a seed-sized Au 56 nanoprism, in which the side Au{100} facets are surrounded by bridging thiolates, whereas the top/bottom {111} facets are capped by phosphine ligands at the corners and Br − at the center. The bromide has been proved to be the key to effectively stabilize the Au{111} to fulfill a complete face-centered-cubic core. In femtosecond electron dynamics analysis, the non-evolution of transient absorption spectra of Au 56 is similar to that of larger-sized gold nanoclusters ( n > 100), which is ascribed to the completeness of the prismatic Au 56 core and an effective electron relaxation pathway created by the stronger Au-Au bonds inside. This work provides some insights for the understanding of plasmonic nanoprism formation.
研究领域:
材料科学
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纳米技术
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物理化学
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DOI
PubMed
高影响因子
Chemical Science
·
2025
·
IF 7.4
Yuping Chen,Guoqing Bian,Zhikun Wu,Qing Tang
Ligand exchange is an important strategy to functionalize metal nanoclusters (NCs) for enhanced properties. Thiolates and alkynyls have been widely used for NC protection, however, the possibility for alkynyl-for-thiolate exchange as well as the kinetics for the ligand exchange process have remained largely unexplored. Herein, we reported the first kinetic investigation into the alkynyl-for-thiolate exchange through the reaction of thiolated Au25(SR)18 with the incoming alkynyl ligands. Interestingly, our simulations revealed the electronic and steric effect of alkynyl ligands, and the precursor cluster’s charge state collectively govern the exchange efficiency and regioselectivity. Notably, the alkynyl-for-thiolate exchange is highly facile when reacting with the nucleophilic lithium or gold(I)−alkynyl complex (Au(C≡CR) or Li(C≡CR)), but fails when using HC≡CR as the exchange ligand. The Au(C≡CPh) complex exhibits charge-state-dependent exchange at the S1 or S2 position, whereas the sterically bulky Au(C≡CtBu) complex decelerates the exchange kinetics and universally targets the S1 position as the exchange product. By contrast, the lithium-alkynyl complex (Li(C≡CPh) or Li(C≡CtBu)) preferentially leads to the S1' exchange isomer, driven by the ionic Li−C bonding that enhances the C≡C π*-electron density and alkynyl nucleophilicity. Our predictions are further validated by the ligand exchange experiments between phenyl ethanethiol (PET) protected [Au25(PET)18]− and Au(C≡CtBu). The electrospray ionization mass spectra (ESI-MS) unambiguously confirms the successful substitution of about 4, 5 and 6 PET ligands by the −C≡CtBu ligand, and the absorption spectrum is drastically changed upon the alkynyl exchange. This work establishes important atomic-level understanding of the alkynyl-for-thiolate exchange mechanism, offering a convenient strategy of realizing alkynyl and thiolate co-protected gold clusters under mild conditions.
研究领域:
纳米材料
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物理化学
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团簇科学
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材料化学
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表面化学
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产品关联
DOI
PubMed
高影响因子
Separations
·
2025
·Vol. 12
·期 5
·106
·
IF 2.7
Xiaoyun Guo,Junli Wang,Yao Liu,Haojun Zhao,Hui Wang,Wentao Wang,Baole Li,Taihong Yan
Developing a new efficient separation ligand based on the “CHON” principle to address the limitations of phosphorus containing extractants in nuclear fuel reprocessing can help further simplify the process flow and reduce the amount of secondary waste. Building upon this critical need, a novel ligand was developed through a strategic application of the Hard and Soft Acids and Bases (HSAB) theory, integrating a soft donor nitrogen atom into the linear architecture of bis-diglycolamide. This groundbreaking ligand, named N,N′-bis[2-(2-(N,N-dioctylcarbamoyl)ethoxy)ethylacetamido]-N″-diethylenetriamine (TOMDEA-BisDGA), has demonstrated remarkable potential in the extraction of Pu(IV). The study unveils that the ligand demonstrates remarkable selectivity and separation efficiency towards Pu(IV) ions while maintaining an exceptionally low extraction capacity for U(VI) across a wide acidity spectrum of 0.1~6 mol/L. To explain the structure properties of complex formed by the ligand and Pu(IV), a systematic analysis was performed, including slope analysis, proton nuclear magnetic resonance (NMR) titration, and Fourier-transform infrared (FT-IR) spectroscopy. This study explores the coordination and separation behavior of diglycolamide ligands with actinide. This work is expected to provide important information and theoretical bases upon which advanced design and optimization of ligands for high-performance processes for the separation of plutonium might be carried out. Such findings will contribute to the understanding of actinide chemistry and further the design of improved separation methods for nuclear applications.
研究领域:
核化学
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配体设计
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放射化学
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产品关联
DOI
高影响因子
MOLECULES
·
2022
·Vol. 27
·期 5
·1482
·
IF 4.927
Yacong An,Xundou Li,Fengjiao Yao,Jinhong Duan,Xian-Da Yang
The PD-1/PD-L1 pathway blockade can generate a good clinical response by reducing immunosuppression and provoking durable antitumor immunity. In addition to antibodies, aptamers can also block the interaction between PD-1 and PD-L1. For the in vivo application, however, free aptamers are usually too small in size and quickly removed from blood via glomerular filtration. To avoid renal clearance of aptamer, we conjugated the PD-L1 aptamer to albumin to form a larger complex (BSA-Apt) and evaluated whether BSA-Apt would enhance the in vivo antitumor efficacy. The PD-L1 aptamer was thiol-modified and conjugated to the amino group of BSA via a SMCC linker. The average size of BSA-Apt was 11.65 nm, which was above the threshold for renal clearance. Functionally, BSA-Apt retained the capability of the PD-L1 aptamer to bind with PDL1-expressing tumor cells. Moreover, both the free aptamer and BSA-Apt augmented the PBMC-induced antitumor cytotoxicity in vitro. Furthermore, BSA-Apt generated a significantly stronger antitumor efficacy than the free PD-L1 aptamer in vivo without raising systemic toxicity. The results indicate that conjugating the PD-L1 aptamer to albumin may serve as a promising strategy to improve the in vivo functionality of the aptamer and that BSA-Apt may have application potential in cancer immunotherapy.Keywords:PD-L1;aptamer;albumin;BSA-Apt;cancer;immunotherapy
研究领域:
肿瘤学
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免疫学
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产品关联
DOI
PubMed
高影响因子
ACS Applied Materials & Interfaces
·
2019
·
IF 8.456
Wen Zhang,An Bu,Qingyuan Ji,Luofu Min,Song Zhao,Yuxin Wang,Jing Chen
We report a class of pKa-directed, precise incorporation of phosphonate ligands into a zirconium-based metal–organic framework (Zr-MOF), MOF-808, via ligand exchange. By replacing of formate ligands with methylphosphonic acid (MPA), ethanephosphonic acid (EPA), and vinylphosphonic acid (VPA), whose pKa values are slightly higher than that of the benzenetricarboxylic acid (BTC) linker in MOF-808, daughter MOFs can be synthesized without controlling the stoichiometric amounts of added MPA. The methylphosphonate MOFs (808-MPAs) demonstrate high porosities, with only small changes in the pore diameter and specific surface area when compared with the parent MOF-808. PXRD patterns and structure refinements indicate the expansion of the lattice for all MOFs after decorating with methylphosphonate ligands. The XPS spectra reveal a charge redistribution of the Zr6 node after ligand exchange. FTIR and 31P MAS NMR spectra, combined with DFT calculation, suggest that the methylphosphonate ligand is connected to the Zr6 node as CH3P(O)(OZr)(OH) species with an accessible acidic P–OH group. Besides, 808-MPAs demonstrate excellent chemical stability in concentrated HCl, concentrated HNO3, hot water, and 0.2 mol/L trifluoroacetic acid solutions. Impressively, 808-MPAs show ultrafast adsorption performance for uranyl ions using the ion-exchange property of P–OH sites in their cavity environment, with an equilibrium time of 10 min, much quicker than the previous adsorbents. The present study demonstrates a series of important proof-of-concept examples of the pKa-directed Zr-MOFs with tunable phosphonate-terminated ligands, which can extend to other phosphonate-functionalized Zr-based framework platforms in the near future.
研究领域:
材料科学
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环境科学
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化学工程
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产品关联
DOI
PubMed
高影响因子
INORGANIC CHEMISTRY
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2020
·
IF 4.825
Kuan-Guan Liu,Xue-Wen Wei,Fahime Bigdeli,Xue-Mei Gao,Jing-Zhe Li,Xiao-Wei Yan,Mao-Lin Hu,Ali Morsali
Advancement of the synthesis and control of the self-assembly process of new high-nucleus silver clusters with desired structures is important for both the material sciences and the many applications. Herein, three new silver clusters, 20-, 22-, and 8-nucleus, based on alkynyl ligands were constructed and their structures were confirmed by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analyses, and Fourier-transform infrared spectroscopy (FT-IR). For the first time, the trivalent tetrahedron anion of AsO43–, as a template, and the surface ligand of Ph2PO2H, with new coordination modes, were employed in preparation of the silver clusters. The role of surface ligands and template anions in the size and structure of the clusters was investigated. The presence of the template in the structure of the clusters led to the formation of the high-nucleus clusters. Also, in this report, it was shown that the participation of the template in the assembly of a cluster can be controlled by the surface ligands. UV–vis absorption and luminescent properties of the clusters and the thermal stability of the 8-nucleus cluster were also studied.
研究领域:
材料科学
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化学合成
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配位化学
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产品关联
DOI
PubMed
高影响因子
Journal of Physical Chemistry C
·
2023
·
IF 3.7
Jifeng Yuan,Jianjun Tian
Perovskite quantum dots (PQDs) have gained significant attention due to their exceptional optical and electronic properties, rendering them promising materials for various optoelectronic applications, such as single-junction solar cells because of the multiple exciton generation effects. To improve the electrical properties of CsPbI3 PQDs, ligand engineering was explored by introducing short-chain ligands to exchange the original long-chain ligands on the PQD surface during the purification process. However, the short-chain ligands suffer from low solubility in the anti-solvent, resulting in insufficient ligand exchange. To address this issue, we developed an in-situ ligand exchange (ILE) strategy to promote the replacement of long-chain ligands with short-chain ones, leading to improved surface chemistry. In this work, 4-methoxyphenethylammonium iodide (CH3O-PEAI) was demonstrated as the short-chain ligand in the ILE strategy, thereby modifying halide vacancy trap states, and promoting carrier transportation and extraction. As a result, the ILE-CsPbI3-based solar cells achieved a higher power conversion efficiency of 14.4% with a high open circuit voltage (VOC) of 1.23 V and exceptional long-term durability due to higher hydrophobicity.
研究领域:
材料科学
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能源技术
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产品关联
DOI
高影响因子
RUSSIAN JOURNAL OF GENERAL CHEMISTRY
·
2021
·Vol. 90
·期 12
·2376-2380
·
IF 0.868
Abbas N.,Shabir G.,Saeed A.,Tirmizi S. A.,Echeverría G. A.,Piro O. E.,Erben M. F.
Abstract The present study is devoted to the synthesis of 4-chloro-2-{[5-(diethylamino)-2-hydroxybenzylidene]amino}phenol and its transition metal complexes. Synthesis of the ligand has been achieved by the condensation reaction of N,N -diethylsalicylaldehyde with 4-chloro-2-aminophenol in acidic medium. Metals complexes of the ligand with different transition metal ions [M 2+ = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II), and Pd(II)] have been accumulated in alcoholic media and characterized by spectroscopic methods. UV-Vis analysis of the complexes indicates the ligand coordination to the metal ions via both OH groups and the azomethine nitrogen atom, acting as a tridentate ligand. Anticancer tests of selected complexes demonstrate moderate in vitro activity of Cu(II) complex against HeLa cell line.
研究领域:
无机化学
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药物化学
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生物无机化学
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DOI
高影响因子
DALTON TRANSACTIONS
·
2015
·Vol. 44
·期 37
·16486-16493
·
IF 4.197
Aixiang Tian,Yali Ning,Yang Yang,Xue Hou,Jun Ying,Guocheng Liu,Juwen Zhang,Xiuli Wang
By using mixed rigid and flexible organic ligands, three Keggin based compounds, [Ag6(tbz)4(bmz)2(H3PW12O40)]·4H2O (1), [Ag(H2bdpm)2(H2PMo12O40)]·7.5H2O (2), and [Ag4(tbz)2(H2bdpm)2(HPMo12O40)]·2H2O (3) (Htbz = thiabendazole, Hbmz = benzimidazole, H2bdpm = 1,1′-bis(3,5-dimethyl-1H-pyrazolate)methane), were hydrothermally synthesized and structurally characterized. Through adopting rigid Htbz ligands, compound 1 with hexa-nuclear AgI clusters has been obtained. These hexa-nuclear clusters are linked by Keggin anions alternately to form a one dimensional (1D) chain. In compound 2, the organic moiety is the flexible H2bdpm ligand. The Keggin anions are fused by [Ag(H2bdpm)2]+ subunits to form a 1D chain. In compound 3, the rigid Htbz and the flexible H2bdpm cooperate to modify the anions. Two tbz and two H2bdpm are fused by four AgI ions to construct a tetra-nuclear AgI cycle. The anions connect these cycles through Ag–O bonds alternately to form a 1D chain. Adjacent chains arrange parallel to build a 2D layer. The chains in the adjacent layers are vertically packed and linked by Ag–O bonds to construct a 3D framework. The electrochemical and photocatalytic properties of the title compounds have been studied. Furthermore, we have also studied the Hg2+ recognition properties in a suspension of compounds 1 and 3.
研究领域:
无机化学
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材料科学
·
分析化学
✓ 已验证
DOI
PubMed
高影响因子
MICROPOROUS AND MESOPOROUS MATERIALS
·
2025
·
IF 4.7
Yujie Zhang,Wenmei Zhang,Guang Yang,Zhihao Chen,Wenhua Zhang
A series of copper triazolate metal-organic frameworks (MOFs), denoted as CuTz-1_X (X = CH 2 OH, Py, and FPh), were synthesized via doping functionalized triazole ligands (3,5-R 2 -tzH where R = CH 2 OH, Py, or FPh) into the reactant of parent CuTz-1 ([Cu 8 (3,5-Ph 2 -tz) 6 ](BF 4 ) 2 (CH 3 OH), where 3,5-Ph 2 -tz = 3,5-diphenyl-1,2,4-trizolate). The synthesized MOFs were thoroughly characterized via PXRD, 1 H NMR, SEM-EDS, EA, TG, etc. It was observed that doping ligands featuring similar size and structure with 3,5-diphenyl-1,2,4-triazole in the parent MOF CuTz-1 resulted in a higher incorporation quantity. Furthermore, the introduction of functional ligands into the modified MOFs, CuTz-1_X, led to enhanced adsorption performance for the removal of methyl blue (MeB) in comparison with that observed over the parent MOF. Especially, CuTz-1_Py, in which 3,5-bis(4-pyridinyl)-1,2,4-triazole was doped, exhibited the highest MeB adsorption capacity of 352.3 mg·g − 1 at 293 K. Besides, the adsorption capacity of MeB over CuTz-1_X MOFs materials maintained stable even in the simulated real water systems. More importantly, the adsorption efficiency of MeB over CuTz-1_Py was still 87 % after four cycles of adsorption experiments while preserving the crystallinity and morphology of the adsorbent, indicating that the modified MOFs materials (i.e. CuTz-1_X) could be promising candidates for wastewater treatment.
研究领域:
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）