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971.
Noncovalent complexes of DNA and Hoechst 33258 were investigated by ESI-FT/ICR MS in various activation modes (collision-induced dissociation (CID), sustained off-resonance irradiation collision-induced dissociation (SORI-CID), infrared multiphoton dissociation (IRMPD) and electron detachment dissociation (EDD)). The binding selectivity of Hoechst 33258 was confirmed by the comparative study of its noncovalent association with different DNA sequences. The CID spectra of [ds + HO - 5H](5-) obtained with a linear hexapole ion trap resulted in unzipping of the strands. This outcome is a clue to the drug-binding mode, shading light on the localization of the binding sites of Hoechst 33258 to the DNA sequence. The IRMPD and SORI-CID experiments mainly gave DNA backbone cleavages and internal fragment ions. From this result, information on the localization of the binding sites of Hoechst 33258 in the DNA sequence was obtained. No sodium cationization was observed on the DNA sequence ions although they were present on fragmentation of the duplex, indicating that the backbone cleavages were generated from the single strand associated with the Hoechst 33258 where the number of alkali cation is restricted. Under electron detachment (ED) conditions, multiple EDs were achieved for the [ds + HO - 5H](5-) ion without any significant dissociation. The presence of drug appears to enhance the stability of the multiply charged system. It was proposed that the studied noncovalent complex involved the formation of zwitterions and consequently strong salt-bridge interactions between DNA and drug. 相似文献
972.
Qin B Chen X Fang X Shu Y Yip YK Yan Y Pan S Ong WQ Ren C Su H Zeng H 《Organic letters》2008,10(22):5127-5130
Introduction of a continuous hydrogen-bonding network suppressed the conformational flexibility of an oligomeric backbone. Cyclization of a rigidified, suitably sized oligomer led to a circular aromatic pentamer. Its crystal structure determined by X-ray crystallography reveals a pseudo five-fold symmetric planarity in the solid state, which is quite unusual among all the previously described shape-persistent macrocycles and synthetic foldamers with biased conformations enforced by noncovalent forces. 相似文献
973.
In order to improve the performance of inorganic/organic composites, aluminum trihydroxide (ATH) core composites with a styrene‐ethylene‐butadiene‐styrene block copolymer grafted with maleic anhydride (MAH‐g‐SEBS) shell phase, and P‐N flame retardant as a synergistic agent, were prepared through an interface design. The effects of polyethylene glycol (PEG) content on the interfacial interaction, flame retardancy, thermal properties, and mechanical properties of high‐density polyethylene (HDPE)/ATH composites were investigated by small angle X‐ray diffraction, rotational rheometer, limiting oxygen index, thermogravimetric analysis (TGA), and tensile testing. The ATH synergistic effects of P‐N flame‐retardant improved the combustion performance of HDPE/ATH/PEG(3%)/MAH‐g‐SEBS/P‐N (abbreviated as HDPE/MH3/M‐g‐S/P‐N) composite by forming more carbon layer, increased the elongation at break from 21% to 558% compared to HDPE/ATH, and increased the interface thickness from 0.447 to 0.891 nm. SEM results support the compatibility of ATH with HDPE increased and the interfacial effect was enhanced. TGA showed the maximum decomposition temperature of the two stages and the yield of the residue at high temperature increased first and then decreased with the increase of PEG content. Rheological behavior showed the storage modulus, complex viscosity, and the relaxation time initially increased and then decreased with the increase of PEG content indicating PEG, M‐g‐S, and ATH powder gradually formed a partial coating, then a full coating, and finally an over‐coated core‐shell structured model. 相似文献
974.
Igor A. Kaltashov Anton El Khoury Chengfeng Ren Sergey N. Savinov 《Journal of mass spectrometry : JMS》2020,55(2)
Ruthenium is a platinoid that exhibits a range of unique chemical properties in solution, which are exploited in a variety of applications, including luminescent probes, anticancer therapies, and artificial photosynthesis. This paper focuses on a recently demonstrated ability of this metal in its +3 oxidation state to form highly stable complexes with tris (hydroxymethyl)aminomethane (H2NC(CH2OH)3, Tris‐base or T) and imidazole (Im) ligands, where a single RuIII cation is coordinated by two molecules of each T and Im. High‐resolution electrospray ionization mass spectrometry (ESI MS) is used to characterize RuIII complexes formed by placing a RuII complex [(NH3)5RuIICl]Cl in a Tris buffer under aerobic conditions. The most abundant ionic species in ESI MS represent mononuclear complexes containing an oxidized form of the metal, ie, [XnRuIIIT2 – 2H]+, where X could be an additional T (n = 1) or NH3 (n = 0‐2). Di‐ and tri‐metal complexes also give rise to a series of abundant ions, with the highest mass ion representing a metal complex with an empirical formula Ru3C24O21N6H66 (interpreted as cyclo(T2RuO)3, a cyclic oxo‐bridged structure, where the coordination sphere of each metal is completed by two T ligands). The empirical formulae of the binuclear species are consistent with the structures representing acyclic fragments of cyclo(T2RuO)3 with addition of various combinations of ammonia and dioxygen as ligands. Addition of histidine in large molar excess to this solution results in complete disassembly of poly‐nuclear complexes and gives rise to a variety of ionic species in the ESI mass spectrum with a general formula [RuIIIHiskTm (NH3)n ? 2H]+, where k = 0 to 2, m = 0 to 3, and n = 0 to 4. Ammonia adducts are present for all observed combinations of k and m, except k = m = 2, suggesting that [His2RuIIIT2 ? 2H]+ represents a complex with a fully completed coordination sphere. The observed cornucopia of RuIII complexes formed in the presence of histidine is in stark contrast to the previously reported selective reactivity of imidazole, which interacts with the metal by preserving the RuT2 core and giving rise to a single abundant ruthenium complex (represented by [Im2RuIIIT2 ? 2H]+ in ESI mass spectra). Surprisingly, the behavior of a hexa‐histidine peptide (HHHHHH) is similar to that of a single imidazole, rather than a single histidine amino acid: The RuT2 core is preserved, with the following ionic species observed in ESI mass spectra: [HHHHHH·(RuIIIT2)m ? (3m‐1)H]+ (m = 1‐3). The remarkable selectivity of the imidazole interaction with the RuIIIT2 core is rationalized using energetic considerations at the quantum mechanical level of theory. 相似文献
975.
Kun Lu Ju Huang Li Ren Chao Li Yejun Guan Bingwen Hu Hao Xu Jingang Jiang Yanhang Ma Peng Wu 《Angewandte Chemie (International ed. in English)》2020,59(15):6258-6262
Precisely controlled crystal growth endows zeolites with special textural and catalytic properties. A nanosheet mordenite zeolite with a thickness of ca. 11 nm, named as MOR‐NS, has been prepared using a well‐designed gemini‐type amphiphilic surfactant as bifunctional structure‐directing agent (SDA). Its benzyl diquarternary ammonium cations structurally directed the formation of MOR topology, whereas the long and hydrophobic hexadecyl tailing group prevented the extensive crystal growth along b axis. This kind of orientated crystallization took place through the inorganic–organic interaction between silica species and SDA molecules present in the whole process. The thin MOR nanosheets, with highly exposed (010) planes and 8‐membered ring (MR) windows, exhibited a much improved ethylene selectivity (42.1 %) for methanol‐to‐olefin (MTO) reactions when compared with conventional bulk MOR crystals (3.3 %). 相似文献
976.
Xiaokai Ding Dong Luo Jiaxiang Cui Huixian Xie Qingqing Ren Zhan Lin 《Angewandte Chemie (International ed. in English)》2020,59(20):7778-7782
Voltage decay and capacity fading are the main challenges for the commercialization of Li‐rich Mn‐based layered oxides (LLOs). Now, a three‐in‐one surface treatment is designed via the pyrolysis of urea to improve the voltage and capacity stability of Li1.2Mn0.6Ni0.2O2 (LMNO), by which oxygen vacancies, spinel phase integration, and N‐doped carbon nanolayers are synchronously built on the surface of LMNO microspheres. Oxygen vacancies and spinel phase integration suppress irreversible O2 release and help lithium ion diffusion, while N‐doped carbon nanolayer mitigates the corrosion of electrolyte with excellent conductivity. The electrochemical performance of LMNO after the treatment improves significantly; the capacity retention rate after 500 cycles at 1 C is still as high as 89.9 % with a very small voltage fading rate of 1.09 mV cycle?1. This three‐in‐one surface treatment strategy can suppress the voltage decay and capacity fading of LLOs. 相似文献
977.
Huiyun Jiang Yameng Ren Weiwei Zhang Yongzhen Wu Etienne Christophe Socie Brian Irving Carlsen Jacques‐E. Moser He Tian Shaik Mohammed Zakeeruddin Wei‐Hong Zhu Michael Grtzel 《Angewandte Chemie (International ed. in English)》2020,59(24):9324-9329
Dye‐sensitized solar cells (DSSCs) based on CuII/I bipyridyl or phenanthroline complexes as redox shuttles have achieved very high open‐circuit voltages (VOC, more than 1 V). However, their short‐circuit photocurrent density (JSC) has remained modest. Increasing the JSC is expected to extend the spectral response of sensitizers to the red or NIR region while maintaining efficient electron injection in the mesoscopic TiO2 film and fast regeneration by the CuI complex. Herein, we report two new D‐A‐π‐A‐featured sensitizers termed HY63 and HY64 , which employ benzothiadiazole (BT) or phenanthrene‐fused‐quinoxaline (PFQ), respectively, as the auxiliary electron‐withdrawing acceptor moiety. Despite their very similar energy levels and absorption onsets, HY64 ‐based DSSCs outperform their HY63 counterparts, achieving a power conversion efficiency (PCE) of 12.5 %. PFQ is superior to BT in reducing charge recombination resulting in the near‐quantitative collection of photogenerated charge carriers. 相似文献
978.
Qingju Wang Tian Ke Lifeng Yang Zhaoqiang Zhang Xili Cui Zongbi Bao Qilong Ren Qiwei Yang Huabin Xing 《Angewandte Chemie (International ed. in English)》2020,59(9):3423-3428
The separation of xenon/krypton (Xe/Kr) mixture is of great importance to industry, but the available porous materials allow the adsorption of both, Xe and Kr only with limited selectivity. Herein we report an anion‐pillared ultramicroporous material NbOFFIVE‐2‐Cu‐i (ZU‐62) with finely tuned pore aperture size and structure flexibility, which for the first time enables an inverse size‐sieving effect in separation along with record Xe/Kr selectivity and ultrahigh Xe capacity. Evidenced by single‐crystal X‐ray diffraction, the rotation of anions and pyridine rings upon contact of larger‐size Xe atoms adapts cavities to the shape/size of Xe and allows strong host‐Xe interaction, while the smaller‐size Kr is excluded. Breakthrough experiments confirmed that ZU‐62 has a real practical potential for producing high‐purity Kr and Xe from air‐separation byproducts, showing record Kr productivity (206 mL g?1) and Xe productivity (42 mL g?1, in desorption) as well as good recyclability. 相似文献
979.
Jun‐Chao Liu Wei‐Qiang Liao Peng‐Fei Li Yuan‐Yuan Tang Xiao‐Gang Chen Xian‐Jiang Song Han‐Yue Zhang Yi Zhang Yu‐Meng You Ren‐Gen Xiong 《Angewandte Chemie (International ed. in English)》2020,59(9):3495-3499
Molecular ferroelectrics have attracted considerable interests because of their easy and environmentally friendly processing, low acoustical impedance and mechanical flexibility. Herein, a molecular thermochromic ferroelectric, N,N′‐dimethyl‐1,4‐diazoniabicyclo[2.2.2]octonium tetrachlorocuprate(II) ([DMe‐DABCO]CuCl4) is reported, which shows both excellent ferroelectricity and intriguing thermochromism. [DMe‐DABCO]CuCl4 undergoes a ferroelectric phase transition from Pca21 to Pbcm at a significantly high Curie temperature of 413 K, accompanied by a color change from yellow to red that is due to the remarkable deformation of [CuCl4]2? tetrahedron, where the ferroelectric and paraelectric phases correspond to yellow and red, respectively. Combined with multiple bistable physical properties, [DMe‐DABCO]CuCl4 would be a promising candidate for next‐generation smart devices, and should inspire further exploration of multifunctional molecular ferroelectrics. 相似文献
980.
Lanfang Ren Jia Lv Hui Wang Yiyun Cheng 《Angewandte Chemie (International ed. in English)》2020,59(12):4711-4719
Cytosolic protein delivery is a prerequisite for the development of protein therapeutics that act on intracellular targets. Proteins are generally membrane‐impermeable and thus need a carrier such as a polymer to facilitate their internalization. However, the efficient binding of proteins with different isoelectric points to polymeric carriers is challenging. In this study, we designed a coordinative dendrimer to solve this problem. The dendrimers modified with dipicolylamine/zinc(II) complex were capable of binding proteins through a combination of ionic and coordination interactions. The best polymer efficiently delivered 30 cargo proteins and peptides into the cytosol, while maintaining their bioactivity after intracellular release. The removal or replacement of zinc ions in the polymer with other transition‐metal ions lead to significantly decreased efficiency in cytosolic protein delivery. This study provides a new strategy to develop robust and efficient polymers for cytosolic protein delivery. 相似文献