摘要：
Pd/SSZ-13 has been proposed as a passive NOx adsorber (PNA) to effectively alleviate NOx emission during vehicle cold start. However, the chemical poisons which are derived from biodiesel and lubricant oil are challenging for the practical application of PNA technology. In this paper, Pd/SSZ-13 was poisoned by alkali/alkaline earth metals to investigate the effects of chemical poisons on the adsorption performance of Pd/SSZ-13. It was found that the alkali/alkaline earth metals led to the decrease of surface area and Brønsted acid sites of Pd/SSZ-13. Strikingly, the 27Al MAS NMR demonstrated that the alkali/alkaline earth metals could effectively prevent Pd/SSZ-13 from dealumination during hydrothermal aging treatment. The H2-TPR results showed that more than 70% of Pd2+ ions were lost in the Na- and K-impregnated Pd/SSZ-13, while almost complete loss of Pd2+ ions was observed in the Mg- and Ca-impregnated Pd/SSZ-13, which resulted in the deactivation of Pd/SSZ-13. Further, the DRIFTS results showed that Mg2+ and Ca2+ ions exhibited preferential substitution for Pd2+ ions, while Na+ and K+ ions preferentially replaced the H+ ions. This work provides insights into the effects of alkali/alkaline earth metals on Pd/SSZ-13, expecting to attract attention to design PNA materials with resistance to chemical poisons.
期刊：
Journal of Materials Science,2023年58(31):12764-12774 ISSN：0022-2461
通讯作者：
Cao, Y;Chen, DD
作者机构：
[Cao, Y; Asibaike, Laizaiti; Mukerabigwi, Jean Felix; Wu, Xuelin; Cao, Yu; Qu, Jiaying; Sun, Yuyang; Huang, Xueying] Cent China Normal Univ, Coll Chem, Key Lab Pesticide & Chem Biol, Minist Educ, Wuhan 430079, Peoples R China.;[Chen, Didi; Qu, Jiaying] Hubei Univ Educ, Hubei Key Lab Purificat & Applicat Plant Anticanc, Wuhan 430205, Peoples R China.;[Mukerabigwi, Jean Felix] Univ Rwanda, Coll Sci & Technol, Dept Chem, POB 3900, Kigali, Rwanda.
通讯机构：
[Cao, Y ] C;[Chen, DD ] H;Cent China Normal Univ, Coll Chem, Key Lab Pesticide & Chem Biol, Minist Educ, Wuhan 430079, Peoples R China.;Hubei Univ Educ, Hubei Key Lab Purificat & Applicat Plant Anticanc, Wuhan 430205, Peoples R China.
摘要：
Due to its small particle size, high specific surface area, functional capability and long-term stable fluorescence, nanodiamond (ND) has been widely used in biomedical applications including fluorescent probes, drug delivery and biological imaging. Nevertheless, the metabolism of ND and its derivatives is not yet well understood for diverse biomedical applications. In this study, to evaluate the cytotoxicity and biodistribution of the ND derivative, pure ND was functionalized with ethylenediamine (EDA) as a linker (ND-EDA) and then covalently labeled with an organic fluorescent dye called calcein. The modified ND is referred to as ND-EDA-calcein. Even at the maximum dose of 0.1 mg & BULL;mL(-1), the in vitro results for ND-EDA-calcein against HepG2 and LO2 cell lines showed negligible cytotoxicity, which was in line with the in vivo observations. In addition, it was found that following an intraperitoneal injection, ND-EDA-calcein could be accumulated mostly in the liver and kidney of the mice but not in the spleen. It is interesting to note that after 5 days following intraperitoneal injection, mice can totally metabolize the elimination of ND-EDA-calcein outside of their bodies. Therefore, our findings suggested that NDs can be considered for various nanomedicine applications including drug delivery and biomarkers.
作者：
Song, Yongjun;Yu, Renyou;Meng, Xianwen;He, Lei
期刊：
Dyes and Pigments,2023年208:110876 ISSN：0143-7208
通讯作者：
He, Lei(helei@ccnu.edu.cn)
作者机构：
[Song, Yongjun; Meng, Xianwen; He, Lei; Yu, Renyou] Cent China Normal Univ, Coll Chem, Key Lab Pesticide & Chem Biol, Minist Educ,Hubei Int Sci & Technol Cooperat Base, Wuhan 430079, Peoples R China.;[He, Lei] South China Univ Technol, State Key Lab Luminescent Mat & Devices, Guangzhou 510640, Peoples R China.
通讯机构：
[Lei He] K;Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, Hubei International Scientific and Technological Cooperation Base of Pesticide and Green Synthesis, College of Chemistry, Central China Normal University, Wuhan, 430079, PR China<&wdkj&>State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou, 510640, PR China
作者机构：
[Cheng, Ying; Xiao, Wen-Jing; Chen, Jia-Rong; Shi, De-Qing; Li, Tian-Tian; Chen, JR] Cent China Normal Univ, Coll Chem, Engn Res Ctr Photoenergy Utilizat Pollut Control &, 152 Luoyu Rd, Wuhan 430079, Hubei, Peoples R China.;[Xiao, Wen-Jing] Shanghai Inst Organ Chem, State Key Lab Organometall Chem, 345 Lingling Rd, Shanghai 200032, Peoples R China.
通讯机构：
[Shi, DQ; Chen, JR ] C;Cent China Normal Univ, Coll Chem, Engn Res Ctr Photoenergy Utilizat Pollut Control &, 152 Luoyu Rd, Wuhan 430079, Hubei, Peoples R China.
摘要：
Radical Cross‐CouplingA copper‐catalyzed enantioselective three‐component radical relay 1,2‐alkylesterification of 1,3‐dienes using cycloalkyl hydroperoxides and carboxylic acids was reported. This protocol features broad substrate scope and good functional group tolerance with respect to each component, providing practical access to a variety of distally keto‐functionalized chiral allylic esters with high enantioselectivity under mild and redox‐neutral conditions. Abstract Transition‐metal‐catalyzed radical relay cross‐coupling reactions of 1,3‐dienes have recently emerged as one of the most powerful methods for construction of structurally diverse allylic compound in a single chemical step. However, there still has been limited success in expanding substrate scope of radical precursors and coupling partners, as well as exploring catalytic asymmetric variants. Herein, we report a copper‐catalyzed enantioselective three‐component 1,2‐alkylesterification of 1,3‐dienes using cycloalkyl hydroperoxides as the carbonyl‐containing alkyl radical sources and carboxylic acids as O‐nucleophiles under mild and redox‐neutral conditions. This protocol features broad substrate scope and good functional group tolerance with respect to each component, providing practical access to a variety of distally keto‐functionalized allylic esters with high enantioselectivity. Mechanistic studies suggest the involvement of a sequential radical relay and C−O cross‐coupling in this three‐component radical reaction.
期刊：
JOURNAL OF ORGANIC CHEMISTRY,2023年88(11):7463-7468 ISSN：0022-3263
通讯作者：
Ke Gao
作者机构：
[Gao, Ke; Sun, Yulin] Cent China Normal Univ, CCNU uOttawa Joint Res Ctr, Key Lab Pesticide & Chem Biol, Minist Educ,Coll Chem, Wuhan 430079, Hubei, Peoples R China.
通讯机构：
[Ke Gao] C;CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079, P. R. China
摘要：
An inexpensive and efficient aminoguanidine-catalyzed reductive cyclization of o-phenylenediamines with CO2 in the presence of triethoxysilane is described. Various functionalized benzimidazoles, benzoxazole, and benzothiazole were synthesized in high yields. Mechanistic studies indicate that formic acid as a cocatalyst promotes the cyclization reaction.
通讯机构：
[Lingling Feng] K;Key Laboratory of Pesticide & Chemical Biology (CCNU), Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, China
摘要：
The frequency and intensity of harmful cyanobacterial blooms (HCBs) are increasing all over the world, their prevention and control have become a great challenge. In this paper, a series of 1,3,4-thiadiazole thioacetamides (T series) were designed and synthesized as potential algaecides. Among them, the compound T3 showed its best algacidal activity against Synechocystis sp. PCC 6803 (PCC 6803, EC50 = 1.51 mu M) and Microcystis aeruginosa FACHB 905 (FACHB905, EC50 = 4.88 mu M), which was more effective than the lead compound L1 (PCC6803, EC50 = 7.7 mu M; FACHB905, EC50 = 8.8 mu M) and the commercially available herbicide prometryn (PCC6803, EC50 = 4.64 mu M;FACHB905, EC50 = 6.52 mu M). Meanwhile, T3 showed a lower inhibitory activity (EC50 = 12.76 mu M) than prometryn (EC50 = 7.98 mu M) to Chlorella FACHB1227, indicating that T3 had selective inhibition to prokaryotic algae (PCC6803, FACHB905) and eukaryotic algae (FACHB1227). Furthermore, the algacidal and anti-algae activities of T3 were significantly better than those of prometryn, while the toxicity of zebrafish and human cells was less than prometryn. Electron microscope, physiological, biochemical and metabonomic anal-ysis showed that T3 interfered with light absorption and light conversion during photosynthesis by significantly reducing chlorophyll content, thus inhibited metabolic pathways such as the Calvin cycle and TCA cycle, and eventually led to the cell rupture of cyanobacteria. These results afforded further development of effective and safe algaecides.
摘要：
Accelerating the migration of interfacial carriers ina heterojunctionis of paramount importance for driving high-performance photoelectricresponses. However, the inferior contact area and large resistanceat the interface limit the eventual photoelectric performance. Herein,we fabricated an S-scheme heterojunction involving a 2D/2D dual-metalloporphyrinmetal-organic framework with metal-center-regulated CuTCPP-(Cu)/CuTCPP-(Fe)through electrostatic self-assembly. The ultrathin nanosheet-likearchitectures reduce the carrier migration distance, while the similarporphyrin backbones promote reasonable interface matching through pi-pi conjugation, thereby inhibiting the recombinationof photogenerated carriers. Furthermore, the metal-center-regulatedS-scheme band alignments create a giant built-in electric field, whichprovides a huge driving force for efficient carrier separation andmigration. Coupling with the biomimetic catalytic activity of CuTCPP-(Fe),the resultant heterojunction was utilized to construct photoelectrochemicaluric acid biosensors. This work provides a general strategy to enhancephotoelectric responses by engineering the interfacial structure ofheterojunctions.
通讯机构：
[Hongwei Sun; Zhihui Ai] K;Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, Institute of Environmental Chemistry, Central China Normal University, Wuhan 430079, PR China
关键词：
Heterogeneous fenton reaction;Oxalic acid;Proton transfer;Thiamphenicol;Zero-valent iron
摘要：
Heterogeneous Fenton reactions of zero-valent iron (ZVI) requires the sufficient release of Fe(II) to catalyze the H(2)O(2) decomposition. However, the rate-limiting step of proton transfer through the passivation layer of ZVI restricted the Fe(II) release via Fe(0) core corrosion. Herein we modified the shell of ZVI with highly proton-conductive FeC(2)O(4)·2H(2)O by ball-milling (OA-ZVI(bm)), and demonstrated its high heterogeneous Fenton performance of thiamphenicol (TAP) removal, with 500 times enhancement of the rate constant. More importantly, the OA-ZVI(bm)/H(2)O(2) showed little attenuation of the Fenton activity during 13 successive cycles, and was applicable across a wide pH range of 3.5-9.5. Interestingly, the OA-ZVI(bm)/H(2)O(2) reaction showed pH self-adapting ability, which initially reduced and then sustained the solution pH in the range of 3.5-5.2. The abundant intrinsic surface Fe(II) of OA-ZVI(bm) (45.54% vs. 27.52% in ZVI(bm), according to Fe 2p XPS profiles) was oxidized by H(2)O(2) and hydrolyzed to generate protons, and the FeC(2)O(4)·2H(2)O shell favored the fast transfer of protons to inner Fe(0), therefore, the consumption-regeneration cycle of protons were accelerated to drove the production of Fe(II) for Fenton reactions, demonstrated by the more prominent H(2) evolution and nearly 100% H(2)O(2) decomposition by OA-ZVI(bm). Furthermore, the FeC(2)O(4)·2H(2)O shell was stable and slightly decreased from 1.9% to 1.7% after the Fenton reaction. This study clarified the significance of proton transfer on the reactivity of ZVI, and provided an efficient strategy to achieve the highly efficient and robust heterogeneous Fenton reaction of ZVI for pollution control.
作者机构：
[Chen, Yuanxing; Xu, Wentao; Wen, Jing; Peng, Xiang; Hu, Liuyong; Xiao, Runshi] Wuhan Inst Technol, Hubei Engn Technol Res Ctr Optoelect & New Energy, Hubei Key Lab Plasma Chem & Adv Mat, Wuhan 430205, Peoples R China.;[Qin, Ying; Zhu, Chengzhou; Chen, Yuanxing; Gu, Wenling; Liu, Mingwang; Gu, WL; Xiao, Runshi; Tan, Rong] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensing Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;[Yu, Han] Hong Kong Univ Sci & Technol, Energy Inst, Guangdong Hong Kong Macao Joint Lab Optoelect & Ma, Dept Chem,Kowloon, Clear Water Bay, Hong Kong 999077, Peoples R China.;[Yu, Han] Hong Kong Univ Sci & Technol, Hong Kong Branch, Chinese Natl Engn Res Ctr Tissue Restorat & Recons, Kowloon, Clear Water Bay, Hong Kong 999077, Peoples R China.
通讯机构：
[Hu, LY ] W;[Gu, WL ] C;Wuhan Inst Technol, Hubei Engn Technol Res Ctr Optoelect & New Energy, Hubei Key Lab Plasma Chem & Adv Mat, Wuhan 430205, Peoples R China.;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensing Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.
摘要：
The intelligent molecular design of organic semiconductors allows for the introduction of specific moieties with recognition functions, while the recognition reactions are largely overlooked for constructing an advanced photoelectrochemical sensor. For the first time, a photoelectrochemical sensing platform for urease detection based on organic semiconductor heterojunction (PM6‐Y6) is constructed benefiting from the selective chemical reactivity of its organic building blocks. Abstract Non‐fullerene acceptors (NFAs) are a crucial component of organic photovoltaics, and they have gained significant attention due to their outstanding photoelectric conversion efficiency. However, the recognition reactions of specific building blocks in NFAs are largely overlooked in the construction of photoelectrochemical (PEC) biosensing platforms. In this study, the potential of Y6, a prototype NFA, is explored to construct a sensitive PEC biosensor for monitoring urease activity due to the selective chemical reactivity of its organic building blocks. The resultant biosensor relies on the urease‐mediated enzymatic reaction, which produces OH− anions that act as a nucleophilic reagent for the linkage of C═C in the Y6 moiety. This results in the formation of Y6‐OH, which exhibits a depressive photoelectric response due to the destroyed conjugated structure and intramolecular charge transfer. As expected, a linear relationship is observed between the recession of photoelectric performance and the concentration of urease, with good sensitivity and selectivity. Furthermore, urease activity detection is also successfully realized in human saliva samples, suggesting the promising potential of NFA‐based PEC biosensors for clinical applications even in the absence of common biological recognition units.
作者机构：
[Zhang Bingwen; Yang Wenchao] Cent China Normal Univ, Natl Key Lab Green Pesticide, Key Lab Pesticide Chem Biol, Minist Educ, Wuhan 430079, Peoples R China.;[Wang Xiaofeng] Univ Chinese Acad Sci, Hangzhou Inst Adv Study, Sch Chem & Mat Sci, Hangzhou 310024, Peoples R China.;[Wang Xiaofeng; Xue Yanqing; Lin Yuqi; Liu Wen; Wang Jing] Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Bioorgan & Nat Prod Chem, Shanghai 200032, Peoples R China.
通讯机构：
[Wang, XF; Liu, W ] C;[Wang, XF ] U;Univ Chinese Acad Sci, Hangzhou Inst Adv Study, Sch Chem & Mat Sci, Hangzhou 310024, Peoples R China.;Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Bioorgan & Nat Prod Chem, Shanghai 200032, Peoples R China.
期刊：
ACS CHEMICAL BIOLOGY,2023年18(4):915-923 ISSN：1554-8929
通讯作者：
Jun Guo
作者机构：
[Zhang, Zhi-Ming; Zhang, Ru-Yan; Feng, Ran-Ran; Ding, Dong; Wen, Yu; Guo, Jun; Zhou, Shi-Hao] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensing Technol &, Hubei Int Sci & Technol Cooperat Base Pesticide &, Wuhan 430079, Peoples R China.;[Wei, Hua-Wei] Jiangsu East Mab Biomed Technol Co Ltd, Nantong 226499, Peoples R China.
通讯机构：
[Jun Guo] K;Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, International Joint Research Center for Intelligent Biosensing Technology and Health, Hubei International Scientific and Technological Cooperation Base of Pesticide and Green Synthesis, College of Chemistry, Central China Normal University, Wuhan 430079, China
摘要：
Modification of antigens to improve their immunogenicity represents a promising direction for the development of protein vaccine. Here, we designed facilely prepared adjuvant-free vaccines in which the N-glycan of SARS-CoV-2 receptor-binding domain (RBD) glycoprotein was oxidized by sodium periodate. This strategy only minimally modifies the glycans and does not interfere with the epitope peptides. The RBD glycoprotein oxidized by high concentrations of periodate (RBD(HO)) significantly enhanced antigen uptake mediated by scavenger receptors and promoted the activation of antigen-presenting cells. Without any external adjuvant, two doses of RBD(HO) elicited 324- and 27-fold increases in IgG antibody titers and neutralizing antibody titers, respectively, compared to the unmodified RBD antigen. Meanwhile, the RBD(HO) vaccine could cross-neutralize all of the SARS-CoV-2 variants of concern. In addition, RBD(HO) effectively enhanced cellular immune responses. This study provides a new insight for the development of adjuvant-free protein vaccines.
作者机构：
[Xu, Yuling; Sun, Yao; Li, Chonglu; Yang, Jingfang] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Key Lab Pesticides & Chem Biol,Minist Educ, Wuhan 430079, Peoples R China.;[An, Jusung; Kim, Jong Seung] Korea Univ, Dept Chem, Seoul 02841, South Korea.;[Ma, Xin] Hubei Univ, Key Lab Synth & Applicat Organ Funct Mol, Minist Educ, Wuhan 430062, Peoples R China.;[Luo, Lishi] Hunan Univ, State Key Lab Chemo Biosensing & Chemometr, Changsha 410082, Peoples R China.;[Deng, Yun] Jianghan Univ, Key Lab Optoelect Chem Mat & Devices, Minist Educ, Wuhan 430056, Peoples R China.
通讯机构：
[Jong Seung Kim] D;[Yao Sun] K;Department of Chemistry, Korea University, Seoul, Republic of Korea<&wdkj&>Key Laboratory of Pesticides and Chemical Biology, Ministry of Education, International Joint Research Center for Intelligent Biosensor Technology and Health, College of Chemistry, Central China Normal University, Wuhan, China
摘要：
Although metal-based chemical agents have demonstrated promising bacteriostatic effects in phototherapy, their short excitation/emission wavelengths and inadequate phototherapy efficiencies make their application in vivo difficult. We therefore synthesized a novel Pt(II) metallacycle (Pt1110) that can be activated with a 980 nm laser for photodiagnosis/treatment in deep tissue. We found that Pt1110 significantly improved photothermal conversion (95% improvement) and O-1(2) generation (phi(& UDelta;) 75% increase) compared to the ligand itself 1 and was well capable of light-induced sterilization under safe laser irradiation (0.72 W/cm(2)). In addition, Pt1110 has little to no toxicity to cells. After incorporated into liposome, Pt1110 NPs was effective in wound healing in infection and keratitis models upon laser irradiation, which was accurately observed by NIR-II fluorescence imaging. This novel metal-coordinated supramolecular material has a potential to become a universal platform for phototherapy in deep tissue.
作者机构：
[Zhang, Zhi-Han; Lu, Liang-Qiu; Yu, Xu-Hui; Xiao, Wen-Jing; Shi, De-Qing] Cent China Normal Univ, Coll Chem, Key Lab Pesticide & Chem Biol, Minist Educ, 152 Luoyu Rd, Wuhan 430079, Hubei, Peoples R China.;[Xiao, Wen-Jing] Shanghai Inst Organ Chem, State Key Lab Organometall Chem, 345 Lingling Rd, Shanghai 200032, Peoples R China.
通讯机构：
[De-Qing Shi] K;Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079, China
摘要：
The asymmetric Michael addition of phosphorus nucleophiles to electron-deficient alkenes is one of the most direct and atom-economical methods to provide chiral organophosphorus compounds with high efficiency in recent years. Herein, we report a cobalt-catalyzed imidazolyl-directed asymmetric phospha-Michael-type reaction of diarylphosphine oxides with electron-deficient alkenes for synthesizing chiral organophosphorus compounds in moderate to good yields and good to excellent enantioselectivities (25 examples, up to 99% yield, and 99% ee). This protocol features broad substrate scope, good functional group tolerance, and mild conditions as well as avoids the release of massive metal wastes and the use of noble transition metal catalysts. The excellent enantioselectivity of the phospha-Michael reaction can be due to the adoption of a novel chiral N4-ligand. Furthermore, the DFT calculation indicates that the bulky 2,4,6-(i-Pr)3C6H2 group of the ligand induces large steric hindrance which blocks the nucleophilic attack from the Si-face.
作者机构：
[Lu, Liang-Qiu; Rao, Li; Wang, Bao-Cheng; Qu, Bao-Le; Xiao, Wen-Jing; Xiong, Fen-Ya] Cent China Normal Univ, Minist Educ, CCNU Ottawa Joint Res Ctr, Coll Chem,Key Lab Pesticide & Chem Biol, 152 Luoyu Rd, Wuhan 430079, Hubei, Peoples R China.;[Tan, Ying; Fang, Kai-Xin; Feng, Ying] Tsinghua Univ, Tsinghua Shenzhen Int Grad Sch, State Key Lab Chem Oncogen, Key Lab Chem Biol, Shenzhen, Peoples R China.;[Lu, Liang-Qiu] Chinese Acad Sci, Lanzhou Inst Chem Phys LICP, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China.;[Lu, Liang-Qiu] Henan Normal Univ, Sch Chem & Chem Engn, Xinxiang 453007, Henan, Peoples R China.
通讯机构：
[Prof. Ying Tan] S;[Prof. Liang-Qiu Lu] C;CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, 430079 Wuhan, Hubei, P. R. China<&wdkj&>State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, 730000 Lanzhou, P. R. China<&wdkj&>School of Chemistry and Chemical Engineering, Henan Normal University, 453007 Xinxiang, Henan, China<&wdkj&>State Key Laboratory of Chemical Oncogenomics, Key Laboratory of Chemical Biology, Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen, P. R. China
关键词：
Antitumor Activity;Aza-Ortho-Quinone Methide;Aza-Sulfur Ylide;Azaheterocycle;Transition Metal Catalysis
摘要：
Metal-polarized aza-ortho-quinone methides (aza-o-QMs) are a unique and efficient handle for azaheterocycle synthesis. Despite great achievements, the potential of these reactive intermediates has not yet been fully exploited, especially the new reaction modes. Herein, we disclosed an unprecedented dearomatization process of metal-polarized aza-o-QMs, affording transient dearomatized spiroaziridine intermediates. Based on this serendipity, we accomplished three sequential dearomatization-rearomatization reactions of benzimidazolines with aza-sulfur ylides, enabling the divergent synthesis of bis-nitrogen heterocycles with high efficiency and flexibility. Moreover, experimental and theoretical studies were performed to explain the proposed mechanisms and observed selectivity. Further cellular evaluation of the dibenzodiazepine products identified a hit compound for new antitumor drugs.
作者机构：
[Zhu, Xinrui; Jia, Shuwen; Li, Dongfeng; Li, DF] Cent China Normal Univ, Coll Chem, Key Lab Pesticide & Chem Biol, Minist Educ, Wuhan 430079, Peoples R China.
通讯机构：
[Li, DF ] C;Cent China Normal Univ, Coll Chem, Key Lab Pesticide & Chem Biol, Minist Educ, Wuhan 430079, Peoples R China.
摘要：
A key challenge in the design of magnetic molecules with intramolecular charge transfer behavior is to obtain reversible magnetic bistability triggered by external stimuli. Here, we show that two dinuclear metal complexes, [(bbp)Fe(CN)3Mn(Py5Me2)]center dot 2.5CH3OH (4) and [(bbp)Fe(CN)3Ni(Py5Me2)]center dot 2.5CH3OH (5) (Py5Me2 = 2,6-bis(1,1-di(pyridine-2-yl)ethyl)pyridine, H2bbp = 2,6-bis(benzimidazole-2-yl)pyridine), were self-assembly synthesized by (Bu4N)2[(bbp)FeIII(CN)3] and [Mn(Py5Me2)(OH2)](ClO4)2 or [Ni(Py5Me2)(OH2)](ClO4)2, respectively. Complexes 4 and 5 exhibited intramolecular metal-to-metal charge transfer with the addition of acids or bases in solution by UV-visible spectrophotometric measurements and electrochemistry studies, and concomitant switching of the {FeIII(mu-CN)MnII/NiII} state to the {FeII(mu-CN)MnIII/NiIII} state. The possibility of external stimulus induced intra-molecular metal-to-metal charge transfer by protonation in [(bbp)Fe(CN)3Mn(Py5Me2)]center dot 2.5CH3OH and [(bbp)Fe(CN)3Ni(Py5Me2)]center dot 2.5CH3OH molecules was investigated.
作者机构：
[Yip, Tsz Chun; Bendel, Lars Eric; Dai, Wei-Min; Sit, Man Ki; Wu, Yan-Dong; Zhang, Wen] Hong Kong Univ Sci & Technol, Hong Kong Branch, Southern Marine Sci & Engn Guangdong Lab Guangzhou, Hong Kong, Peoples R China.;[Yip, Tsz Chun; Bendel, Lars Eric; Dai, Wei-Min; Sit, Man Ki; Wu, Yan-Dong; Zhang, Wen] Hong Kong Univ Sci & Technol, Dept Chem, Lab Adv Catalysis & Synth, Kowloon, Hong Kong, Peoples R China.;[Cao, Hui Hui] Southern Med Univ, Sch Tradit Chinese Med, Guangzhou 510515, Peoples R China.;[Wu, Yan-Dong] Cent China Normal Univ, Coll Chem, Wuhan 430079, Hubei, Peoples R China.
通讯机构：
[Wei-Min Dai] H;Hong Kong Branch of the Southern Marine Science and Engineering Guangdong Laboratory (Guangzhou), and Laboratory of Advanced Catalysis and Synthesis, Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong SAR P. R. of China
摘要：
Synthesis of the C19-truncated maltepolide E has been accomplished via a diene–ene ring-closing metathesis (RCM) strategy without damage to the C11–C14 alkenyl epoxy unit. Upon release of the C17-OH group, it attacked at the C14 position with double bond migration and epoxide ring opening to furnish the C19-truncated maltepolides A and B as proposed for the biosynthesis of maltepolides.
作者机构：
[Tang, Yuchen; Gao, Tingjuan; Zheng, Xingxing] Cent China Normal Univ, Coll Chem, China Key Lab Pesticide & Chem Biol, Minist Educ, Wuhan 430079, Peoples R China.
通讯机构：
[Tang, YC; Gao, TJ ] C;Cent China Normal Univ, Coll Chem, China Key Lab Pesticide & Chem Biol, Minist Educ, Wuhan 430079, Peoples R China.
摘要：
High-throughput assays play an important role in the fields of drug discovery, genetic analysis, and clinical diagnostics. Although super-capacity coding strategies may facilitate labeling and detecting large numbers of targets in a single assay, practically, the constructed large-capacity codes have to be decoded with complicated procedures or are lack of survivability under the required reaction conditions. This challenge results in either inaccurate or insufficient decoding outputs. Here, we identified chemical-resistant Raman compounds to build a combinatorial coding system for the high-throughput screening of cell-targeting ligands from a focused 8-mer cyclic peptide library. The accurate in situ decoding results proved the signal, synthetic, and functional orthogonality for this Raman coding strategy. The orthogonal Raman codes allowed for a rapid identification of 63 positive hits at one time, evidencing a high-throughput-out capability in the screening process. We anticipate this orthogonal Raman coding strategy being generalized to enable efficient high-throughput-out screening of more useful ligands for cell targeting and drug discovery.
通讯机构：
[Yin, B ] N;[Li, DF ] C;Cent China Normal Univ, Coll Chem, Key Lab Pesticide & Chem Biol, Minist Educ, Wuhan 430079, Peoples R China.;Northwest Univ, Coll Chem & Mat Sci, Lab Theoret Mol Magnetism LTMM, Xian 710127, Peoples R China.
摘要：
An air-stable Dy-III complexwith a hexagonalbipyramid D (6h) symmetry derived of a neutralhexaaza macrocyclic Schiff base ligand shows zero-field single-moleculemagnet behavior with an open magnetic hysteresis loop up to 13 K andthe effective barrier of 584 K. Thedesign and synthesis of air-stable single-molecule magnets(SMMs) with large effective barriers of magnetic reversal and remarkablyslow relaxation times are challenging. The design and synthesis ofair-stable complexes with large effective magnetic reversal barriersand remarkably slow relaxation times are challenging in the fieldof SMMs. Herein, we present an air-stable hexagonal bipyramid [Dy-III(bpyN4)(Ph3SiO)(2)](BPh4)(1) (bpyN4 = neutral hexaaza macrocyclic Schiff baseligand derived of 6,6 & PRIME;-diformyl-2,2 & PRIME;-bipyridyl and triethylenetetramine).The magnetic data demonstrate that the complex shows zero-field SMMbehavior with magnetic hysteresis loops up to 13 K and an effectivebarrier of 584 K for 1. The experimental effective barrieris close to the energy of the first excited Kramers doublet (E (KD1)) obtained from ab initio calculations.
通讯机构：
[Zhang, AD ] C;Cent China Normal Univ, Minist Educ, Coll Chem, Key Lab Pesticide & Chem Biol, Wuhan 430079, Peoples R China.
摘要：
We report herein a dynamic facet-selective capping (dFSC) strategy for α-calcium sulfate hemihydrate crystal growth from dihydrate gypsum in the presence of a catechol-derived PEI capping agent (DPA-PEI) with inspiration by the biomineralization process of mussel. The crystal shape is controllable and varies from long and pyramid-tipped prisms to thin hexagonal plate. The highly uniform truncated crystals have extremely high compression and bending strengths after hydration molding.
