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121.
Harri Räisälä Dr. Tuomas Lönnberg 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(18):4751-4756
An 11-mer oligonucleotide incorporating a central (2-iodobenzoylamino)methyl residue has been synthesized and palladated by oxidative addition of Pd2(dba)3. UV melting profiles of the duplexes formed by the palladated oligonucleotide with its natural complements were biphasic and the higher melting temperatures (Tm) exhibited considerable hysteresis. CD spectra, in turn, resembled those of canonical B-type double helices. Two-step denaturation, with the “low-Tm” melting involving only canonical base pairs and the “high-Tm” melting involving also dissociation of a PdII-mediated base pair, appears the most likely explanation for the observed UV melting profiles. As the latter step in all cases takes place at a higher temperature than denaturation of natural duplexes of the same length, the putative PdII-mediated base pairs are stabilizing. 相似文献
122.
Xin Dong Juan Yang Xiao-Ting Zheng Yan Chen Li-Hong Ye Bin Wang Hui Zheng Jun Cao Qiu-Yan Wang Yu-Han Hu 《Electrophoresis》2020,41(1-2):123-130
A novel micro matrix solid phase dispersion method was successfully used for the extraction of quaternary alkaloids in Phellodendri chinensis cortex. The elution of target compounds was accomplished with sodium hexanesulfonate as the eluent solvent. A neutral ion pair was formed between ion-pairing reagent and positively charged alkaloids in this process, which was beneficial for selectively extraction of polar alkaloids. Several parameters were optimized and the optimal conditions were listed as follows: silica gel as the sorbent, silica to sample mass ratio of 1:1, the grinding time of 1 min. The exhaustive elution of targets was achieved by 200 µL methanol/water (9:1) containing 150 mM sodium hexane sulfonate at pH 4.5. The method validation covered linearity, recovery, precision of intraday and interday, limits of detection, limits of quantitation, and repeatability. This established method was rapid, simple, environmentally friendly, and highly sensitive. 相似文献
123.
Tae Hee Kim Hyun Mo Lee Hee Soo Park Sung Dong Kim Su Jin Kwon Atsushi Tahara Hideo Nagashima Bun Yeoul Lee 《应用有机金属化学》2019,33(4)
The original Sasol catalytic system for ethylene tetramerization is composed of a Cr source, a PNP ligand, and MAO (methylaluminoxane). The use of expensive MAO in excess has been a critical concern in commercial operation. Many efforts have been made to replace MAO with non‐coordinating anions (e.g., [B(C6F5)4]?); however, most of such attempts were unsuccessful. Herein, an extremely active catalytic system that avoids the use of MAO is presented. The successive addition of two equivalent [H(OEt2)2]+[B(C6F5)4]? and one equivalent CrCl3(THF)3 to (acac)AlEt2 and subsequent treatment with a PNP ligand [CH3(CH2)16]2C(H)N(PPh2)2 ( 1 ) yielded a complex presumably formulated as [ 1 ‐CrAl (acac)Cl3(THF)]2+[B(C6F5)4]?2, which exhibited high activity when combined with iBu3Al (1120 kg/g‐Cr/h; ~4 times that of the original Sasol system composed of Cr (acac)3, iPrN(PPh2)2, and MAO). Via the introduction of bulky trialkylsilyl substituents such as –SiMe3, –Si(nBu)3, or –SiMe2(CH2)7CH3 at the para‐position of phenyl groups in 1 (i.e., by using [CH3(CH2)16]2C(H)N[P(C6H4‐p‐SiR3)2]2 instead of 1 ), the activities were dramatically improved, i.e., tripled (2960–3340 kg/g‐Cr/h; more than 10 times that of the original Sasol system). The generation of significantly less PE (<0.2 wt%) even at a high temperature is another advantage achieved by the introduction of bulky trialkylsilyl substituents. NMR studies and DFT calculations suggest that increase of the steric bulkiness on the alkyl‐N and P‐aryl moieties restrict the free rotation around (alkyl)N–P (aryl) bonds, which may cause the generation of more robust active species in higher proportion, leading to extremely high activity along with the generation of a smaller amount of PE. 相似文献
124.
利用期权契约所建立的政企合作储备应急物资模式能够有效解决政府单独储备模式所造成的物资储备量过少或过多而引起的困境。然而由于应急物资的需求特性,若应急物资供应企业采用按单生产方式安排生产储备计划,势必会造成库存水平升高,引发资金周转困难等问题,对政企之间的长期合作造成不利影响。基于此,本文设计了基于供应方生产能力的应急物资生产模型。该模型在政府利用批发价格契约与期权契约采购应急物资的基础上,研究了供应方根据自身生产能力进行柔性生产时的生产与储备问题。通过推导政企双方最优决策后,重点分析了期权权利金,执行价格,加急生产成本等参数对供应方生产决策的影响,并证明与按单生产模式相比,柔性生产模式可有效降低供应方的库存量与生产成本,提高其利润,继而提高整体供应链的利润水平,有助于促进政企之间长期稳定的合作。 相似文献
125.
Empirical potential structure refinements have been made to recent high-energy x-ray diffraction data, providing molecular models of deeply supercooled water. The average O-O coordination number is found to drop from 5.13 at 293?K to 4.85 at 244?K, within 3.5?Å. Triplet O-O-O bond angle distributions reveal a broad peak centred at 96.4° at 293?K which shifts to 100.0° at 244?K, indicative of the local geometry becoming increasingly tetrahedral with decreasing temperature. However, although the number of non-bonded interstitial molecules between the first and second shells is depleted upon cooling, the number of interstitial molecules forming triplets that are embedded within the hydrogen bonded tetrahedral network at θOOO?=?53°, remains constant. This is consistent with previous observations of an invariant O-O coordination number with temperature (4.24 out to 3.3?Å) and corresponds to non-bonded molecules positioned at close to half the ideal tetrahedral angle. Both -O-O-O- and hydrogen-bonded -O-H-O- ring length distributions show increases in 6 and 7-membered rings upon supercooling. This is concomitant with a shift and increase in intensity of peaks at r4 ~8.7?Å and r5 ~10.8?Å in the oxygen-oxygen pair distribution function, which in the models correspond to correlations between adjacent and next-nearest-neighbour hydrogen-bonded rings. 相似文献
126.
K.C. Devarayapalli S.V. Prabhakar Vattikuti T.V.M. Sreekanth Ki Soo Yoo P.C. Nagajyothi Jaesool Shim 《应用有机金属化学》2020,34(3):e5376
Herein, cobalt (Co)-based metal–organic zeolitic imidazole frameworks (ZIF-67) coupled with g-C3N4 nanosheets synthesized via a simple microwave irradiation method. SEM, TEM and HR-TEM results showed that ZIF-67 were uniformly dispersed on g-C3N4 surfaces and had a rhombic dodecahedron shape. The photocatalytic properties of g-C3N4/ZIF-67 nanocomposite were evaluated by photocatalytic dye degradation of crystal violet (CV), 4-chlorophenol (4-CP) and photocatalytic hydrogen (H2) production. In presence of visible light illumination, the photocatalytic dye results showed that 95% CV degradation and 53% 4-CP degradation within 80 min. The H2 production of the g-C3N4/ZIF-67 composite was 2084 μmol g−1, which is 3.84 folds greater than that of bare g-C3N4 (541 μmol g−1). 相似文献
127.
Dr. Xiaoming Jie Dr. Qiu Sun Dr. Constantin G. Daniliuc Robert Knitsch Prof. Dr. Michael Ryan Hansen Prof. Dr. Hellmut Eckert Dr. Gerald Kehr Prof. Dr. Gerhard Erker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(6):1269-1273
The active six-membered cyclo-FLP 6 undergoes a rapid P/B addition reaction to carbon dioxide. At elevated temperature, the resulting heterobicyclo[2.2.2]octane derived product 7 undergoes ring opening and equilibrates with the cyclotetramer (7)4 . In the large macrocyclic structure, four monomeric six-membered cyclo-FLP units are connected by four CO2 molecules to form the supramolecular ring system. The P/B cyclo-FLP 6 undergoes a variety of additional cycloaddition reactions. 相似文献
128.
Pham Duy Khanh Tran Hong Mo Trinh T. T. Tran 《Numerical Functional Analysis & Optimization》2019,40(8):924-943
Necessary and sufficient conditions for qualitative properties of infinite dimensional linear programing problems such as solvability, duality, and complementary slackness conditions are studied in this article. As illustrations for the results, we investigate the parametric version of Gale’s example. 相似文献
129.
Multistrain diseases, which are infected through individual contacts, pose severe public health threat nowadays. In this paper, we build competitive and mutative two‐strain edge‐based compartmental models using probability generation function (PGF) and pair approximation (PA). Both of them are ordinary differential equations. Their basic reproduction numbers and final size formulas are explicitly derived. We show that the formula gives a unique positive final epidemic size when the reproduction number is larger than unity. We further consider competitive and mutative multistrain diseases spreading models and compute their basic reproduction numbers. We perform numerical simulations that show some dynamical properties of the competitive and mutative two‐strain models. 相似文献
130.