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排序方式: 共有167条查询结果,搜索用时 15 毫秒
61.
62.
Max S. Coles Gina Quach Dr. Jonathon E. Beves Dr. Evan G. Moore 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(24):9609-9613
The development of photocatalytic reactions has provided many novel opportunities to expand the scope of synthetic organic chemistry. In parallel with progress towards uncovering new reactivity, there is consensus that efforts focused on providing detailed mechanistic insight in order to uncover underlying excited-state reactions are essential to maximise formation of desired products. With this in mind, we have investigated the recently reported sensitization-initiated electron transfer (SenI-ET) reaction for the C−H arylation of activated aryl halides. Using a variety of techniques, and in particular nanosecond transient absorption spectroscopy, we are able to distinguish several characteristic signals from the excited-state species involved in the reaction, and subsequent kinetic analysis under various conditions has facilitated a detailed insight into the likely reaction mechanism. 相似文献
63.
The first use of 2-pyridylcyanoxime, (py)C(CN)NOH, in transition metal chemistry is described. Depending on the nature of the metal starting material and the reaction conditions employed, the Cu(II)/(py)C(CN)NOH system has provided access to complexes [Cu(3)O{(py)C(CN)NO}(3)(NO(3))(H(2)O)(2)(MeOH)] (1), [Cu(4)O{(py)C(CN)NO}(4)(O(2)CMe)(2)] (2), [Cu(4)(OH)(2){(py)C(CN)NO}(2)(O(2)CPh)(4)](2n)·n[Cu(4)(OH)(2){(py)C(CN)NO}(2)(O(2)CPh)(4)] (3), and [Cu{(py)C(CN)NO}(2)](n) (4). The molecule of 1 consists of three Cu(II) atoms in a strictly equilateral arrangement bridged by a central μ(3)-oxide group. The molecule of 2 consists of a tetrahedron of Cu(II) atoms held together by a central μ(4)-oxide ion, four η(1):η(1):η(1):μ-(py)C(CN)NO(-) ligands and two η(1):η(1):μ-MeCO(2)(-) groups. The crystal structure of 3 consists of [Cu(4)(OH)(2){(py)C(CN)NO}(2)(O(2)CPh)(4)](2n) double chains and discrete cluster [Cu(4)(OH)(2){(py)C(CN)NO}(2)(O(2)CPh)(4)] molecules. The crystal structure of 4 consists of neutral polymeric chains based on centrosymmetric mononuclear [Cu{(py)C(CN)NO}(2)] units. The Cu(II) atoms are doubly bridged by the oximate groups of two η(1):η(1):η(1):μ-(py)C(CN)NO(-) ligands. Variable-temperature, solid-state direct current (dc) magnetic susceptibility studies were carried out for 1-4. The data indicate very strong antiferromagnetic exchange interactions for 1-3. The obtained J values are discussed in depth on the basis of the structural parameters of the complexes, literature reports, and existing magnetostructural correlations. 相似文献
64.
65.
Microfluidics made of yarns and knots: from fundamental properties to simple networks and operations 总被引:1,自引:0,他引:1
We present and characterize cotton yarn and knots as building blocks for making microfluidic circuits from the bottom up. The yarn used is made up of 200-300 fibres, each with a lumen. Liquid applied at the extremity of the yarn spontaneously wets the yarn, and the wetted length increases linearly over time in untreated yarn, but progresses according to a square root relationship as described by Washburn's equation upon plasma activation of the yarn. Knots are proposed for combining, mixing and splitting streams of fluids. Interestingly, the topology of the knot controls the mixing ratio of two inlet streams into two outlet yarns, and thus the ratio can be adjusted by choosing a specific knot. The flow resistance of a knot is shown to depend on the force used to tighten it and the flow resistance rapidly increases for single-stranded knots, but remains low for double-stranded knots. Finally, a serial dilutor is made with a web made of yarns and double-stranded overhand knots. These results suggest that yarn and knots may be used to build low cost microfluidic circuits. 相似文献
66.
Mary C. Machado Gina V. Vimbela Michael Nilsson Stephanie Dallaire Rongcong Wu Anubhav Tripathi 《Electrophoresis》2019,40(14):1812-1819
Large‐scale genetic screening of neonatal dried blood spots for episomal DNA has a great potential to lower patient mortality and morbidity through early diagnosis of primary immunodeficiencies. However, DNA extraction from the surface of dried blood spots remains one of the most time consuming, costly, and labor‐intensive parts of DNA analysis. In the present study, we developed and optimized a rapid methodology using only 50 V and heat to extract episomal DNA from dried blood spots prepared from diagnostic cord blood samples. This electric field DNA extraction is the first methodology to use an electric field to extract episomal DNA from a dried blood spot. This 25‐minute procedure has one of the lowest times for the extraction of episomal DNA found within the literature and this novel procedure not only negates the need for costly treatment and wash steps, but reduces the time of manual procedures by more than 30 min while retaining the 75–80% of the yield. Combined with real‐time PCR, this novel method of electric field extraction not only provides an effective tool for the large scale genetic analysis of neonates, but a key step forward in the simplification and standardization of diagnostic testing. 相似文献
67.
Lorine Brülisauer Gina Valentino Sakura Morinaga Kübra Cam Dr. Jens Thostrup Bukrinski Prof. Dr. Marc A. Gauthier Prof. Dr. Jean‐Christophe Leroux 《Angewandte Chemie (International ed. in English)》2014,53(32):8392-8396
Disulfide‐containing IgG‐, Fc‐, or albumin‐based prodrugs that rely on FcRn‐trafficking by endothelial cells for prolonged circulation in the body might be hampered by premature bio‐reduction processes during FcRn‐mediated recycling events. A detailed bio‐reduction analysis of redox‐sensitive albumin conjugates in two FcRn‐expressing cell lines has been performed. The obtained results indicate that the FcRn‐mediated recycling pathway is not (or is only poorly) bio‐reducing. 相似文献
68.
Florio GM Werblowsky TL Müller T Berne BJ Flynn GW 《The journal of physical chemistry. B》2005,109(10):4520-4532
Self-assembled monolayers of chrysene and indene on graphite have been observed and characterized individually with scanning tunneling microscopy (STM) at 80 K under low-temperature, ultrahigh vacuum conditions. These molecules are small, polycyclic aromatic hydrocarbons (PAHs) containing no alkyl chains or functional groups that are known to promote two-dimensional self-assembly. Energy minimization and molecular dynamics simulations performed for small groups of the molecules physisorbed on graphite provide insight into the monolayer structure and forces that drive the self-assembly. The adsorption energy for a single chrysene molecule on a model graphite substrate is calculated to be 32 kcal/mol, while that for indene is 17 kcal/mol. Two distinct monolayer structures have been observed for chrysene, corresponding to high- and low-density assemblies. High-resolution STM images taken of chrysene with different bias polarities reveal distinct nodal structure that is characteristic of the molecular electronic state(s) mediating the tunneling process. Density functional theory calculations are utilized in the assignment of the observed electronic states and possible tunneling mechanism. These results are discussed within the context of PAH and soot particle formation, because both chrysene and indene are known reaction products from the combustion of small hydrocarbons. They are also of fundamental interest in the fields of nanotechnology and molecular electronics. 相似文献
69.
The effect of thickness on the glass transition dynamics in ultra-thin polystyrene (PS) films (4 nm < L < 60 nm) was studied by thin film ac-calorimetry, dielectric spectroscopy (DRS) and capacitive dilatometry (CD). In all PS-films, a prominent α-process was found in both the ac-calorimetric and dielectric response, indicating the existence of cooperative bulk dynamics even in films as thin as 4 nm. Glass transition temperatures (Tg) were obtained from ac-calorimetric data at 40 Hz and from capacitive dilatometry, and reveal a surprising, marginal thickness dependence Tg(L). These results, which confirm recent data by Efremov et al. [Phys. Rev. Lett. 91 (2003)] but oppose many previous observations, is rationalized by differences in film annealing conditions together with the fact that our techniques probe exclusively cooperative dynamics (ac-calorimetry) or allow the effective separation of surface and “bulk”-type mobility (CD). Two other observations, a significant reduction in cp towards lower film thickness and the decrease in the contrast of the dilatometric glass transition, support the idea of a layer-like mobility profile consisting of both cooperative “bulk” dynamics and non-cooperative surface mobility. 相似文献
70.
Mihaela Badea Rodica Olar Gina Vasile Ana Emandi Veronica Pop Dana Marinescu 《Journal of Thermal Analysis and Calorimetry》2005,81(2):273-276
Summary This paper reports the investigation of the thermal stability of three new complexes of Cr(III) with acrylate anion, [Cr2(C3H3O2)4(OH)2(H2O)4], [Cr3O(C3H3O2)6(C3H4O2)3](C3H3O2)×5H2O and [Cr2(C3H3O2)5(OH)] ×2H2O, respectively. This type of complexes is important in proper carbohydrate and lipid metabolism of mammals. The thermal decomposition steps were evidenced. The thermal transformations are complex processes according to TG and DTG curves including dehydration and oxidative degradation of acrylate ion processes. The final product of decomposition is the chromium(III) oxide. 相似文献