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81.
Amarante TR Neves P Tomé C Abrantes M Valente AA Paz FA Pillinger M Gonçalves IS 《Inorganic chemistry》2012,51(6):3666-3676
The reaction of [MoO(2)Cl(2)(di-tBu-bipy)] (1) (di-tBu-bipy = 4,4'-di-tert-butyl-2,2'-bipyridine) with water at 100-120 °C in a Teflon-lined stainless steel autoclave, in an open reflux system, or in a microwave synthesis system gave the octanuclear complex [Mo(8)O(22)(OH)(4)(di-tBu-bipy)(4)] (2) as a microcrystalline powder in good yields. Single crystals of 2 suitable for X-ray diffraction were obtained by the reaction of MoO(3) and di-tBu-bipy in water at 160 °C for 3 days. The molecular structure of 2 comprises a purely inorganic core, Mo(4)O(8)(μ(3)-OH)(2)(μ(2)-O)(2), attached to two peripheral oxo-bridged binuclear units, Mo(2)O(4)(μ(2)-O)(2)(OH)(di-tBu-bipy)(2). The inorganic core is composed of a unique assembly of four {MoO(5)} distorted square pyramids connected to each other via edge-sharing. Overall, the octanuclear complex adopts a highly distorted form strongly resembling an "S"-shaped molecular unit. Complex 2 was applied in the catalytic epoxidation of the biorenewable olefins DL-limonene (Lim) and methyl oleate (Ole), using tert-butylhydroperoxide (TBHP) as an oxygen donor, under mild reaction conditions (55 °C, air). The reactions of Lim and Ole gave the respective epoxide monomers in fairly high selectivities at high conversions (89% 1,2-epoxy-p-menth-8-ene selectivity at 96% Lim conversion; 99% methyl 9,10-epoxystearate selectivity at 94% Ole conversion, reached within 24 h reaction). Iodometric titrations revealed no measurable "non-productive" decomposition of TBHP. 相似文献
82.
This investigation describes the reduction of an aryl thiocyanate with samarium(II) iodide, followed by reaction with various epoxides, to produce β-hydroxy sulfides. This method of ring opening of epoxides provides a substantial improvement in reaction time and convenience over existing methods while maintaining good regioselectivity and excellent yield. 相似文献
83.
Nigel M. Groome Elghareeb E. Elboray Dr. Martyn W. Inman Prof. H. Ali Dondas Dr. Roger M. Phillips Colin Kilner Prof. Ronald Grigg 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(6):2180-2184
Naturally occurring indole‐3‐carbinol and 3,3‐diindolylmethane show bioactivity in a number of disparate disease areas, including cancer, prompting substantial synthetic analogue activity. We describe a new approach to highly functionalised derivatives that starts from allene gas and proceeds via the combination of a three‐component Pd0‐catalysed cascade with a one‐pot, three‐component carbophilic PtII cascade linked to a stereoselective acid‐catalysed Mannich–Michael reaction that generates complex cyclopropyl diindolylmethanes which show selective activity against prostate cancer cell lines. 相似文献
84.
There are many interesting cubic curves which arise from the geometry of the triangle. In particular, those which are invariant under the operation of isogonal conjugacy have attracted much attention, and a class of these is here investigated by a variety of methods. 相似文献
85.
Stevens MM Allen S Sakata JK Davies MC Roberts CJ Tendler SJ Tirrell DA Williams PM 《Langmuir : the ACS journal of surfaces and colloids》2004,20(18):7747-7752
The coiled-coil protein motif occurs in over 200 proteins and has generated interest for a range of applications requiring surface immobilization of the constituent peptides. This paper describes an investigation of the environment-responsive behavior of a monolayer of surface-immobilized artificial proteins, which are known to assemble to form coiled-coil structures in bulk solution. An extended version of the quartz crystal microbalance (QCM-D) and surface plasmon resonance (SPR) are independently employed to characterize the adsorption of the proteins to a gold surface. The data suggest that the molecules arrange in a closely packed layer orientated perpendicular to the surface. QCM-D measurements are also employed to measure pH-induced changes in the resonant frequency (f) and the energy dissipation factor (D) of a gold-coated quartz crystal functionalized with the formed monolayer. Exposure of the protein monolayer to a pH 4.5 solution results in a shift of 43 Hz in f and a shift of -0.7 x 10(-6) in D as compared to pH 7.4. In contrast, increasing the pH to 11.2, results in f and D shifts of -17 Hz and 0.6 x 10(-6), respectively. The magnitude of the observed shifts suggests that the proteins form a rigid layer at low pH that can be hydrated to a fluid layer as the pH is increased. These observations correlate with spectroscopic changes that indicate a reduction in the helical content of the protein in bulk solutions of high pH. 相似文献
86.
Paradigm confirmed: the first use of ionic liquids to dramatically influence the outcome of chemical reactions 总被引:3,自引:0,他引:3
It has been an unproven paradigm that the choice of which ionic liquid to use in a chemical reaction can have a dramatic effect on the outcome of that chemical reaction. We demonstrate, for the first time, that the reaction of toluene and nitric acid in three different ionic liquids gives rise to three completely different products in high yield. Furthermore, ionic liquids can catalyze these reactions with the only byproduct being water. [reaction: see text] 相似文献
87.
Antonova AB Bruce MI Ellis BG Gaudio M Humphrey PA Jevric M Melino G Nicholson BK Perkins GJ Skelton BW Stapleton B White AH Zaitseva NN 《Chemical communications (Cambridge, England)》2004,(8):960-961
Elimination of AuX(PR3)(X = halogen, R = Ph, tol) occurs readily in reactions between compounds containing C(sp)- or C(sp2)-X bonds and alkynyl or polyynyl gold(I) complexes; this reaction has been applied to the syntheses of complexes containing a variety of metal centres linked by C(n) chains (n up to 16). 相似文献
88.
Exposure of dilute solution of bromobenzene and p-dibromobenzene in fluorotrichloromethane to 60Coγ-rays at 77 K gave the corresponding cations characterized by ESR spectra. Estimated spin densities on bromine of ≈ 30% and 23%, respectively, are greater than those predicted by comparison with neutral α-bromo radicals, R2CBr (≈ 15%). Evidence for dimer cation formation in more concentrated solutions is presented. 相似文献
89.
We have investigated the use of supercritical fluids (SCFs) as carriers/solvents during the postsynthesis alumination of mesoporous silica. SCFs were found to be ideally suited for transport of Al into mesoporous silica and to lead to Al-grafted aluminosilicate materials that exhibit exceptional hydrothermal (steam) stability even for highly aluminated materials. The improvements in steam stability arising from the use of SCFs as grafting media (as compared to aqueous or organic solvents) are remarkable, especially for Al-grafted MCM-41 materials with high (Si/Al < or = 10) Al contents. It is proposed that under supercritical fluid conditions Al is sorbed on the surface of the pore walls of the host Si-MCM-41 with little penetration into the pore wall region, that is, the low solvating power of SCFs ensures the deposition of Al onto rather than into the silica framework. This is because the host silica framework cannot undergo any significant hydrolysis (to allow penetration of Al into the pore wall region) during the SCF-mediated alumination. Removal of the Al (i.e., dealumination) which occurs during steaming is therefore less detrimental to the structural integrity of SCF-grafted Al-MCM-41 materials since any dealumination that occurs will not involve removal of Al from deep within the pore walls. 相似文献
90.
The DDQ mediated oxidative cyclisation reactions of a series of dihydronaptho[2,1-b]furans were examined. In the presence of an acid catalyst, the reaction yielded polycyclic ethers and lactones in good to excellent yields. 相似文献