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991.
Enhanced Photodynamic Therapy by Reduced Levels of Intracellular Glutathione Obtained By Employing a Nano‐MOF with CuII as the Active Center 下载免费PDF全文
Dr. Wei Zhang Jun Lu Dr. Xiaonan Gao Dr. Ping Li Dr. Wen Zhang Dr. Yu Ma Dr. Hui Wang Prof. Bo Tang 《Angewandte Chemie (International ed. in English)》2018,57(18):4891-4896
In photodynamic therapy (PDT), the level of reactive oxygen species (ROS) produced in the cell directly determines the therapeutic effect. Improvement in ROS concentration can be realized by reducing the glutathione (GSH) level or increasing the amount of photosensitizer. However, excessive amounts photosensitizer may cause side effects. Therefore, the development of photosensitizers that reduce GSH levels through synergistically improving ROS concentration in order to strengthen the efficacy of PDT for tumor is important. We report a nano‐metal–organic framework (CuII‐metalated nano‐MOF {CuL‐[AlOH]2}n (MOF‐2, H6L=mesotetrakis(4‐carboxylphenyl)porphyrin)) based on CuII as the active center for PDT. This MOF‐2 is readily taken up by breast cancer cells, and high levels of ROS are generated under light irradiation. Meanwhile, intracellular GSH is considerably decreased owing to absorption on MOF‐2; this synergistically increases ROS concentration and accelerates apoptosis, thereby enhancing the effect of PDT. Notably, based on the direct adsorption of GSH, MOF‐2 showed a comparable effect with the commercial antitumor drug camptothecin in a mouse breast cancer model. This work provides strong evidence for MOF‐2 as a promising new PDT candidate and anticancer drug. 相似文献
992.
Cobalt‐Catalyzed Electrophilic Amination of Aryl‐ and Heteroarylzinc Pivalates with N‐Hydroxylamine Benzoates 下载免费PDF全文
Dr. Yi‐Hung Chen Simon Graßl Prof. Dr. Paul Knochel 《Angewandte Chemie (International ed. in English)》2018,57(4):1108-1111
Aryl‐ and heteroarylzinc pivalates can be aminated with O‐benzoylhydroxylamines at 25 °C within 2–4 h in the presence of 2.5–5.0 % CoCl2?2 LiCl to furnish the corresponding tertiary arylated or heteroarylated amines in good yields. This electrophilic amination also provides access to diarylamines and aryl(heteroaryl)amines. A new tuberculosis drug candidate (Q203) was prepared in six steps and 56 % overall yield by using this cobalt‐catalyzed amination as the key step. 相似文献
993.
Total Synthesis of (6R,10R,13R,14R,16R,17R,19S,20R,21R,24S, 25S,28S,30S,32R,33R,34R,36S,37S,39R)‐Azaspiracid‐3 Reveals Non‐Identity with the Natural Product 下载免费PDF全文
Nathaniel T. Kenton Dr. Daniel Adu‐Ampratwum Dr. Antony A. Okumu Dr. Zhigao Zhang Dr. Yong Chen Dr. Son Nguyen Dr. Jianyan Xu Dr. Yue Ding Dr. Pearse McCarron Dr. Jane Kilcoyne Prof. Dr. Frode Rise Prof. Dr. Alistair L. Wilkins Dr. Christopher O. Miles Prof. Dr. Craig J. Forsyth 《Angewandte Chemie (International ed. in English)》2018,57(3):805-809
A convergent and stereoselective total synthesis of the previously assigned structure of azaspiracid‐3 has been achieved by a late‐stage Nozaki–Hiyama–Kishi coupling to form the C21?C22 bond with the C20 configuration unambiguously established from l ‐(+)‐tartaric acid. Postcoupling steps involved oxidation to an ynone, modified Stryker reduction of the alkyne, global deprotection, and oxidation of the resulting C1 primary alcohol to the carboxylic acid. The synthetic product matched naturally occurring azaspiracid‐3 by mass spectrometry, but differed both chromatographically and spectroscopically. 相似文献
994.
Yan‐Long Ma Dr. Hua Ke Dr. Arto Valkonen Prof. Kari Rissanen Prof. Wei Jiang 《Angewandte Chemie (International ed. in English)》2018,57(3):709-713
Positive cooperativity achieved through activating weak non‐covalent interactions is common in biological assemblies but is rarely observed in synthetic complexes. Two new molecular tubes have been synthesized and the syn isomer binds DABCO‐based organic cations with high orientational selectivity. Surprisingly, the ternary complex with two hosts and one guest shows a high cooperativity factor (α=580), which is the highest reported for synthetic systems without involving ion‐pairing interactions. The X‐ray single‐crystal structure revealed that the strong positive cooperativity likely originates from eight C?H???O hydrogen bonds between the two head‐to‐head‐arranged syn tube molecules. These relatively weak hydrogen bonds were not observed in the free hosts and only emerged in the complex. Furthermore, this complex was used as a basic motif to construct a robust [2+2] cyclic assembly, thus demonstrating its potential in molecular self‐assembly. 相似文献
995.
Highly Emissive Fused Heterocyclic Alkynylgold(III) Complexes for Multiple Color Emission Spanning from Green to Red for Solution‐Processable Organic Light‐Emitting Devices 下载免费PDF全文
Dr. Man‐Chung Tang Chin‐Ho Lee Dr. Maggie Ng Yi‐Chun Wong Dr. Mei‐Yee Chan Prof. Dr. Vivian Wing‐Wah Yam 《Angewandte Chemie (International ed. in English)》2018,57(19):5463-5466
A new class of fused heterocyclic tridentate ligand‐containing alkynylgold(III) complexes with tunable emission color has been successfully designed and synthesized. Structural modification of the σ‐donating fused heterocyclic alkynyl ligands, including substituted fluorene, carbazole, and triphenylamine, enables a large spectral shift of about 110 nm (ca. 3310 cm?1) that covers the green to red region to be realized with the same tridentate ligand‐containing alkynylgold(III) complexes in solid‐state thin films. Interestingly, the energy of the excimeric emission can be controlled by the rational design of the fused heterocyclic alkynyl ligands. Superior solution‐processable organic light‐emitting devices (OLEDs) with high external quantum efficiencies (EQEs) of 12.2, 13.5, 9.3, and 5.2 % were obtained with green, yellow, orange, and red emission. These high EQE values are comparable to those of the vacuum‐deposited OLEDs based on structurally related alkynylgold(III) complexes. 相似文献
996.
Barbier–Negishi Coupling of Secondary Alkyl Bromides with Aryl and Alkenyl Triflates and Nonaflates 下载免费PDF全文
Ke‐Feng Zhang Fadri Christoffel Prof. Dr. Olivier Baudoin 《Angewandte Chemie (International ed. in English)》2018,57(7):1982-1986
A mild and practical Barbier–Negishi coupling of secondary alkyl bromides with aryl and alkenyl triflates and nonaflates has been developed. This challenging reaction was enabled by the use of a very bulky imidazole‐based phosphine ligand, which resulted in good yields as well as good chemo‐ and site selectivities for a broad range of substrates at room temperature and under non‐aqueous conditions. This reaction was extended to primary alkyl bromides by using an analogous pyrazole‐based ligand. 相似文献
997.
Peripheral Templation‐Modulated Interconversion between an A4L6 Tetrahedral Anion Cage and A2L3 Triple Helicate with Guest Capture/Release 下载免费PDF全文
Xuemin Bai Prof. Chuandong Jia Prof. Yanxia Zhao Dr. Dong Yang Shi‐Cheng Wang Prof. Anyang Li Prof. Yi‐Tsu Chan Prof. Yao‐Yu Wang Prof. Xiao‐Juan Yang Prof. Biao Wu 《Angewandte Chemie (International ed. in English)》2018,57(7):1851-1855
An anion‐coordination‐based A4L6 (“A” denotes anion and “L” is ligand) tetrahedral cage was constructed by a C2‐symmetric bis‐bis(urea) ligand and phosphate anion, which showed reversible interconversion with the A2L3 triple helicate as a response to the template, concentration, or solvent. Notably, an unusual “peripheral” templation was found to be critical to stabilize the tetrahedral structure. This peripheral effect was utilized to assemble an “empty” A4L6 cage that allows the multi‐stimuli‐controlled capture/release of biologically important species such as choline and acetylcholine. 相似文献
998.
Imaging of Colorectal Cancers Using Activatable Nanoprobes with Second Near‐Infrared Window Emission 下载免费PDF全文
Ge Xu Qinglong Yan Xiaoguang Lv Prof. Ying Zhu Kai Xin Ben Shi Rongchen Wang Jian Chen Wei Gao Prof. Ping Shi Prof. Chunhai Fan Prof. Chunchang Zhao Prof. He Tian 《Angewandte Chemie (International ed. in English)》2018,57(14):3626-3630
Fluorescent probes in the second near‐infrared window (NIR‐II) allow high‐resolution bioimaging with deep‐tissue penetration. However, existing NIR‐II materials often have poor signal‐to‐background ratios because of the lack of target specificity. Herein, an activatable NIR‐II nanoprobe for visualizing colorectal cancers was devised. This designed probe displays H2S‐activated ratiometric fluorescence and light‐up NIR‐II emission at 900–1300 nm. By using this activatable and target specific probe for deep‐tissue imaging of H2S‐rich colon cancer cells, accurate identification of colorectal tumors in animal models were performed. It is anticipated that the development of activatable NIR‐II probes will find widespread applications in biological and clinical systems. 相似文献
999.
Modifying the Steric Properties in the Second Coordination Sphere of Designed Peptides Leads to Enhancement of Nitrite Reductase Activity 下载免费PDF全文
Dr. Karl J. Koebke Dr. Fangting Yu Elvin Salerno Casey Van Stappen Dr. Alison G. Tebo Prof. James E. Penner‐Hahn Prof. Vincent L. Pecoraro 《Angewandte Chemie (International ed. in English)》2018,57(15):3954-3957
Protein design is a useful strategy to interrogate the protein structure‐function relationship. We demonstrate using a highly modular 3‐stranded coiled coil (TRI‐peptide system) that a functional type 2 copper center exhibiting copper nitrite reductase (NiR) activity exhibits the highest homogeneous catalytic efficiency under aqueous conditions for the reduction of nitrite to NO and H2O. Modification of the amino acids in the second coordination sphere of the copper center increases the nitrite reductase activity up to 75‐fold compared to previously reported systems. We find also that steric bulk can be used to enforce a three‐coordinate CuI in a site, which tends toward two‐coordination with decreased steric bulk. This study demonstrates the importance of the second coordination sphere environment both for controlling metal‐center ligation and enhancing the catalytic efficiency of metalloenzymes and their analogues. 相似文献
1000.
Active Intracellular Delivery of a Cas9/sgRNA Complex Using Ultrasound‐Propelled Nanomotors 下载免费PDF全文
Malthe Hansen‐Bruhn Dr. Berta Esteban‐Fernández de Ávila Dr. Mara Beltrán‐Gastélum Prof. Jing Zhao Dr. Doris E. Ramírez‐Herrera Pavimol Angsantikul Prof. Kurt Vesterager Gothelf Prof. Liangfang Zhang Prof. Joseph Wang 《Angewandte Chemie (International ed. in English)》2018,57(10):2657-2661
Direct and rapid intracellular delivery of a functional Cas9/sgRNA complex using ultrasound‐powered nanomotors is reported. The Cas9/sgRNA complex is loaded onto the nanomotor surface through a reversible disulfide linkage. A 5 min ultrasound treatment enables the Cas9/sgRNA‐loaded nanomotors to directly penetrate through the plasma membrane of GFP‐expressing B16F10 cells. The Cas9/sgRNA is released inside the cells to achieve highly effective GFP gene knockout. The acoustic Cas9/sgRNA‐loaded nanomotors display more than 80 % GFP knockout within 2 h of cell incubation compared to 30 % knockout using static nanowires. More impressively, the nanomotors enable highly efficient knockout with just 0.6 nm of the Cas9/sgRNA complex. This nanomotor‐based intracellular delivery method thus offers an attractive route to overcome physiological barriers for intracellular delivery of functional proteins and RNAs, thus indicating considerable promise for highly efficient therapeutic applications. 相似文献