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41.
Frontispiece: Reactivity Study of Pyridyl‐Substituted 1‐Metalla‐2,5‐diaza‐cyclopenta‐2,4‐dienes of Group 4 Metallocenes 下载免费PDF全文
42.
The ground and low-lying excited states of CoCN have been studied by ab initio multireference single and double excitation configuration interaction (MR-SDCI) calculations with Davidson's correction Q and Cowan-Griffin's relativistic corrections. The electronic ground state of CoCN is (3)Phi(i) and the equilibrium geometry is linear with bond lengths of r(e)(Co-C)=1.8540 A and r(e)(C-N)=1.1677 A, substantially different from the experimentally derived values of r(0)(Co-C)=1.8827(7) A and r(0)(C-N)=1.1313(10) A. The first excited state is (3)Delta(i), separated from the ground state by 727 cm(-1). Larger dynamical electron correlation energy for the low-spin (3)Phi state than for the high-spin (5)Phi state makes the (3)Phi state to be the ground state, which is discussed in terms of the differences in natural orbitals. A new spin-orbit interaction scheme between the X (3)Phi(i) and 1 (3)Delta(i) states is proposed. 相似文献
43.
Hungerford G Rei A Ferreira MI Suhling K Tregidgo C 《The journal of physical chemistry. B》2007,111(13):3558-3562
Time-resolved fluorescence anisotropy and fluorescence recovery after photobleaching were applied to study the diffusion of dyes and a fluorescence-labeled enzyme in a sol-gel-derived medium. This type of medium exhibits attractive properties such as robustness, low processing temperature, high porosity, large internal surface area, and can act as protective immobilization media for biologically active molecules. This makes it a suitable candidate for biosensor applications. The glasslike nature and good optical quality allows for light addressable entities to be incorporated and accessed using spectroscopy. This type of matrix, once formed, can be anything from an ordered gel to a robust glassy block depending on the aging process. In this work we apply confocal microscopy and time-resolved fluorescence techniques to study both rotational and lateral diffusion with aging time within a silica sol-gel derived monolith. An enzyme, horseradish peroxidase, was labeled with Alexa Fluor 488 and rotation related to both the enzyme and the probe monitored during the matrix aging process. Diffusion coefficients of between ca. 0.5 x 10(-7) and 4 x 10(-7) cm2 s(-1) were obtained from preliminary FRAP measurements of fluorescein and correlated to differences in the catalytic activity of HRP incorporated in the monolith. 相似文献
44.
Daisuke Nakano Kenji Ishitsuka Madoka Ishihara Ryota Tsuchihashi Masafumi Okawa Kazuo Tamura Junei Kinjo 《Molecules (Basel, Switzerland)》2021,26(24)
During the screening of novel chemotherapeutic candidates from plants against adult T-cell leukemia/lymphoma, we identified that the extracts of Thuja occidentalis (Cupressaceae) showed potent anti-proliferative activity in MT-1 and MT-2 cells. Therefore, we attempted to isolate the active components from this plant. We isolated and identified 32 compounds (1–32; eight lignans, 18 terpenoids, and six flavonoids) from the extracts of the leaves and cones. Their structures were determined by spectroscopic analysis. Several of the isolated compounds inhibited the growth of both cell lines. Lignans showed more potent activity than other classes of compounds. A comparison of the activities of compounds 1–8 revealed that the presence of a trans-lactone (linkage of C-6 to C-7) correlated with increased activity. Diterpenes showed moderate activity, and the presence of a ketone moiety at the C-7 position correlated with increased activity in compounds 12–21. In addition, biflavones showed moderate activity, and the presence of methoxy functions appeared to influence the activity of these compounds. Several lignans were lead compound of anti-cancer reagent (etoposide). In conclusion, not only lignans, but also diterpenes and/or biflavones, may be promising candidates for the treatment of adult T-cell leukemia/lymphoma. 相似文献
45.
PEG‐400[poly(ethylene glycol‐400)] is used as a “green” recyclable solvent in the one‐pot synthesis of quinoxalines by reaction with aryl ketones, hypervalent Iodine(III) Sulfonate, and o‐phenylenediamines. Significant rate enhancements and improved yields have been observed. 相似文献
46.
Simon Reitz Menekse Cebi Philipp Reiß Gregor Studnik Uwe Linne Ulrich Koert Prof. Dr. Lars‐Oliver Essen Prof. Dr. 《Angewandte Chemie (International ed. in English)》2009,48(26):4853-4857
The attachment of modulators to a trimeric porin ion channel was investigated (see picture of the trimer with a crown ether modulator (orange)). The interplay of modulator and protein is essential for the conformational heterogeneity of the hybrid channel. Single‐site attachment in large pores is not sufficient to change the electrophysiological characteristics of the pores—such change requires additional noncovalent interactions or second‐site attachments.
47.
The DIBAL reduction of 2-phenylethyl 3,3,3-trifluoro-2-methylpropionate 2 at -78 degrees C afforded the aluminum acetal 3, and this intermediate, on worming up to 0 degrees C, was found to slowly decompose into the corresponding aldehyde 4, which smoothly reacted with appropriate nucleophiles in a one-pot manner in good to excellent yields with up to 93% diastereoselectivity. 相似文献
48.
Peter C. Kunz Indre Thiel Anna Louisa Noffke Guido J. Reiß Fabian Mohr Bernhard Spingler 《Journal of organometallic chemistry》2012,697(1):33-40
A variety of piano-stool complexes of cyclopentadienyl ruthenium(II) with imidazole-based PN ligands have been synthesized starting from the precursor complexes [CpRu(C10H8)]PF6, [CpRu(NCMe)3]PF6 and [CpRu(PPh3)2Cl]. PN ligands used are imidazol-2-yl, -4-yl and -5-yl phosphines.Depending on the ligand and precursor different types of coordination modes were observed; in the case of polyimidazolyl PN ligands these were κ1P-monodentate, κ2P,N-, κ2N,N- and κ3N,N,N- chelating and μ-κP:κ2N,N-brigding. The solid-state structures of [CpRu(1a)2Cl ]·H2O (5.H2O) and [{CpRu(μ-κ2-N,N-κ’1-P-2b)}2](C6H5PO3H)2(C6H5PO3H2)2, a hydrolysis product of the as well determined [{CpRu(2b)}2](PF6)2.2CH3CN (7b.2CH3CN) were determined (1a = imidazol-2-yldiphenyl phosphine, 2b = bis(1-methylimidazol-2-yl)phenyl phosphine, 3a = tris(imidazol-2-yl)phosphine). Furthermore, the complexes [CpRu(L)2]PF6 (L = imidazol-2-yl or imidazol-4-yl phosphine) have been screened for their catalytic activity in the hydration of 1-octyne. 相似文献
49.
石墨烯作为一种理想的新型二维纳米材料,有着独特的理化性能和广泛应用价值,但成本高、产率低、分散性较差是制约其推广应用的关键.为了解决这一问题,现以北方杨树叶为原料,以KMnO4和H2SO4为氧化剂,水热氧化裂化直接得到MnO2仿生石墨烯复合材料(MnO2@BGO).通过XPS、SEM、TEM、XRD等测试手段对材料组成及微观结构进行表征.从SEM、TEM及氮气吸附脱附分析可以看出,通过氧化碳化直接得到的MnO2@BGO复合材料,MnO2分布均匀,比表面积达605 m2/g.此复合材料与未经氧化剂浸渍得到碳材料(BGO)相比,更多的保留了叶片原有的叶脉结构和孔隙,孔径分布较窄,平均孔径为3.7nm.从AMF分析可以看出,MnO2@BGO复合材料类似二维纳米膜,得到的片层厚度最薄<1.23 nm,最厚≯5.65 nm,平均厚度2.57 nm.XPS分析表明,C存在形式以C=C为主,表明材料石墨化程度较高,属于仿生石墨烯.电化学性能分析表明,在电流密度在1 A/g时,该材料所做电极比电容为387 F/g. 相似文献
50.