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31.
Sangya Chitranshi Dr. B. Adinarayana Mainak Das Dr. Won-Young Cha Prof. Dr. Dongho Kim Prof. Dr. A. Srinivasan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(56):12911-12915
Three distinct conformational structures of carbaoctaphyrins were prepared by incorporating bis-4,4'-biphenyl units in the macrocyclic core. The free-base form adopts a figure-eight conformation, whereas the protonation triggers a conformational change with a pyrrole ring inversion and acquires an open-framework structure. The insertion of bis-RhI metal ion in the macrocyclic core affords a singly twisted conformational structure. Furthermore, the local aromaticity in the bis-4,4'-biphenyl ring dominates the overall macrocyclic aromaticity in all three forms, and thus adopts nonaromatic characteristics. These results are supported by spectral as well as theoretical studies, and they are unambiguously confirmed by X-ray crystal analyses. 相似文献
32.
Dr. Waqar Rizvi Naxhije Berisha Dr. Christopher Farley Dr. N. V. S. Dinesh K. Bhupathiraju Dr. Chrysafis Andreou Emaad Khwaja German V. Fuentes Dr. Moritz F. Kircher Dr. Ruomei Gao Dr. Charles Michael Drain 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(64):14517-14521
Distortion of nominally planar phthalocyanine macrocycles affects the excited state dynamics in that most of the excited-state energy decays through internal conversion. A click-type annulation reaction on a perfluorophthalocyanine platform appending a seven-membered ring to the β-positions on one or more of the isoindoles distorts the macrocycle and modulates solubility. The distorted derivative enables photoacoustic imaging, photothermal effects, and strong surface-enhanced resonance Raman signals. 相似文献
33.
Giuseppe Spedalotto Dr. Robert Gericke Marta Lovisari Dr. Erik R. Farquhar Dr. Brendan Twamley Dr. Aidan R. McDonald 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(51):11983-11990
Hydroxide-bridged high-valent oxidants have been implicated as the active oxidants in methane monooxygenases and other oxidases that employ bimetallic clusters in their active site. To understand the properties of such species, bis-μ-hydroxo-NiII2 complex ( 1 ) supported by a new dicarboxamidate ligand (N,N′-bis(2,6-dimethyl-phenyl)-2,2-dimethylmalonamide) was prepared. Complex 1 contained a diamond core made up of two NiII ions and two bridging hydroxide ligands. Titration of the 1 e− oxidant (NH4)2[CeIV(NO3)6] with 1 at −45 °C showed the formation of the high-valent species 2 and 3 , containing NiIINiIII and NiIII2 diamond cores, respectively, maintaining the bis-μ-hydroxide core. Both complexes were characterised using electron paramagnetic resonance, X-ray absorption, and electronic absorption spectroscopies. Density functional theory computations supported the spectroscopic assignments. Oxidation reactivity studies showed that bis-μ-hydroxide-NiIII2 3 was capable of oxidizing substrates at −45 °C at rates greater than that of the most reactive bis-μ-oxo-NiIII complexes reported to date. 相似文献
34.
Dr. Chaolu Eerdun Thi Hien Thuy Nguyen Takuya Okayama Satoshi Hisanaga Prof. Dr. Jun-ichiro Setsune 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(22):5777-5786
The hexapyrrole-α,ω-dicarbaldehydes 1 a and 1 b were metallated with CuII, NiII, and PdII to give bimetallic complexes where a pair of 3 N+O four-coordinate metal planes are helically distorted and the central 2,2′-bipyrrole subunit adopts a cis or trans conformation. X-ray crystallographic analysis of the bisCu complex revealed a closed form with a cis-2,2′-bipyrrole subunit and an open form with a trans-2,2′-bipyrrole subunit. The bisPd complexes took a closed form both in the solid state and in solution. They are regarded as single helicates of two turns and the energy barrier for the interchange between an M helix and a P helix was remarkably influenced by the bulky 3,3′-substituent of the central 2,2′-bipyrrole subunit. Although the bisNi complexes adopt a closed form in the solid state, they exist as a homohelical open C2-symmetric form or a heterohelical open Ci-symmetric form in solution. A theoretical study suggested that the closed form of 1 a Pd was stabilized by the Pd–Pd interaction. Compound 1 a Pd was reversibly oxidized by one electron at 0.14 V versus ferrocene/ferrocenium (Fc/Fc+) and this oxidized species showed Vis/NIR absorption bands at λ=767 and 1408 nm. 相似文献
35.
Ping Chen Yanhong Hao Xinxin Wang Prof. Dr. Dan Yuan Prof. Dr. Yingming Yao Prof. Dr. Lutz Ackermann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(30):7292-7297
Highly position selective alkylations of N-alkylindoles at C7-positions have been enabled by cationic zirconium complexes. The strategy provides a straightforward access to install alkyl groups at C7-positions of indoles without a complex directing group. Mechanistic studies provided support for the importance of Brønsted acids in the catalytic manifold. 相似文献
36.
Jiamei Han Dr. Guohai Liang Prof. Da Xing 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(35):8353-8362
Accurate diagnosis of tumor characteristics, including its location and boundary, is of immense value to subsequent therapy. Activatable magnetic resonance imaging (MRI) contrast agents that respond to tumor-specific microenvironments, such as the redox state, pH, and enzyme activity, enable better mapping of tumor tissue. However, the practical application of most reported activatable agents is hampered by problems including potential toxicity, inefficient elimination, and slow activation. In this study, we developed a zwitterionic iron complex (Fe-ZDS) as a positive MRI contrast agent for tumor-specific imaging. Fe-ZDS could dissociate in weakly acidic solution rapidly, accompanied by clear longitudinal relaxivity (r1) enhancement, which enabled the complex to act as a pH-sensitive contrast agent for tumor-specific MR imaging. In vivo experiments showed that Fe-ZDS rapidly enhanced the tumor-to-normal contrast ratio by >40 %, which assisted in distinguishing the tumor boundary. Furthermore, Fe-ZDS circulated freely in the bloodstream and was excreted relatively safely via kidneys owing to its zwitterionic nature. Therefore, Fe-ZDS is an ideal candidate for a tumor-specific MRI contrast agent and holds considerable potential for clinical translation. 相似文献
37.
自由基浓度测定方法的再验证及其在煤化学中应用 《燃料化学学报》2019,47(11):1281-1287
对前人建立的标准曲线法测煤中自由基浓度进行优化,以DPPH标准样品和基准样品的二次积分面积比值为新参数,结果显示新参数标准曲线法的实测值与理论值相对误差都在5%以内;重复性、复现性实验的相对标准偏差都小于3%。将新参数标准曲线法用于分析不同煤化程度煤和新疆黑山煤(HS)沥青质的自由基浓度,发现随着煤化程度增加,其煤中自由基浓度逐渐增大,从低阶褐煤的8.531×10~(17)/g上升到高阶无烟煤3.37899×10~(19)/g;而在HS煤液化过程中,随着加氢液化温度的升高,其沥青质自由基浓度逐渐下降,从290℃的1.5793×10~(18)/g降到450℃的7.410×10~(17)/g,沥青质自由基浓度变化趋势与其产率变化趋势相一致。 相似文献
38.
Prof. Shinji Toyota Dr. Eiji Tsurumaki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(28):6878-6890
Saturn-like systems consisting of nanoscale rings and spheres are fascinating motifs in supramolecular chemistry. Several ring molecules are known to include spherical molecules at the center of the cavity via noncovalent attractive interactions. In this Minireview, we generalize the molecular design, the structural features, and the supramolecular chemistry of such “nano-Saturns”, which consist of monocyclic rings and fullerene spheres (mainly C60), on the basis of previous experimental and theoretical studies. Ring molecules are classified into three types (loop, belt, and disk) according to their shapes and possible interactions. Whereas typical belt-shaped rings tend to form tight complexes due to the wide contact area via π–π interactions, flat disk-shaped rings generally form weak complexes due to the narrow contact area mainly via CH–π interactions. In spite of the small association energies, disk-shaped rings are attractive because such rings can mimic the planet Saturn precisely as exemplified by an anthracene cyclic hexamer–C60 complex. 相似文献
39.
By applying advanced telecommunication solid state devices to microwave (MW) resonant cavity system for flow chemistry, it becomes possible to heat up low polarity solvents higher than 250 C, that are considered impossible to heat up by MW until now. The resonant cavity system is opening new process windows to production processes of specialty chemicals which require low cost, high yield and high productivity. 相似文献
40.
《Acta Crystallographica. Section C, Structural Chemistry》2018,74(9):1045-1052
A new tantalum phosphate, tridecasodium distrontium ditantalum nonaphosphate, Na13Sr2Ta2(PO4)9, was prepared using the high‐temperature flux method. The structure can be described as a three‐dimensional open framework containing isolated [TaV2(PO4)9]17− units that are interlocked by Na and Sr ions. Band structure studies by the first‐principles method revealed that Na13Sr2Ta2(PO4)9 is an insulator with an indirect band gap of 4.78 eV, which makes it suitable as a luminescent host matrix. A series of solid solutions, i.e. Na13Sr2–xTa2(PO4)9:xDy3+ (x = 0.01, 0.02, 0.04, 0.06, 0.08, 0.1, 0.12 and 0.14), were prepared and their photoluminescence properties studied. Under 350 nm light excitation, these emit two typical emissions of the Dy3+ ion, i.e. the 4F9/2→6H15/2 transition centred at 476 nm and the 4F9/2→6H13/2 transition centred at 570 nm. 相似文献