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61.
Mason WR 《Inorganic chemistry》2000,39(2):370-374
Electronic absorption and 8 T magnetic circular dichroism (MCD) spectra are reported for nitrate salts of Pt(AuPPh3)8(2+) and Au(AuPPh3)8(3+) in poly(methyl methacrylate) (PMM) thin films at 295 and 10 K in the vis-UV region from 1.6 to 3.6 microm(-1) (1 microm(-1) = 10(4) cm(-1). Enhanced resolution is observed at low temperature, especially for Pt(AuPPh3)8(2+), which emphasizes the differences in the nature of the low-energy excited configurations and states between Pt(AuPPh3)8(2+) and Au(AuPPh3)8(3+). The absorption and MCD spectra for Pt(AuPPh3)8(2+) are interpreted in terms of a combination of excitations from filled Pt 5d orbitals to empty Au framework 6s orbitals and intraframework Au8(2+) (IF) transitions, whereas the spectra for Au(AuPPh3)8(3+) are ascribed entirely to Au IF transitions. 相似文献
62.
Turner DR Henry M Wilkinson C McIntyre GJ Mason SA Goeta AE Steed JW 《Journal of the American Chemical Society》2005,127(31):11063-11074
Four isomorphous complexes of formula [M(L)(4)(H(2)O)(2)]SO(4).2H(2)O (M = Co, 1a; Ni, 1b; Cu, 1c; Zn, 1d) have been isolated and characterized by single-crystal X-ray diffraction and neutron diffraction using the quasi-Laue diffractometer VIVALDI at the Institut Laue-Langevin as well as by thermogravimetric analysis. The structures contain a discrete, strongly hydrogen-bonded water tetramer which causes a significant distortion of the metal coordination sphere in each case. Partial atomic charges and hardness analysis (PACHA) calculations reveal that the shortest hydrogen bonds are not the strongest in this constrained, cyclic solid-state structure and show that the distortion at the metal center is caused by the drive to maintain the integrity of the water tetramer. The system undergoes a disorder-order transition on slow cooling that provides insight into the nature of communication between water squares. 相似文献
63.
M. M. Mason J. S. Morris V. L. Spate C. K. Baskett T. A. Nichols T. L. Horsman L. Le Marchand L. N. Kolonel S. Yukimoto 《Journal of Radioanalytical and Nuclear Chemistry》1998,232(1-2):29-34
Haem peroxidases are globular proteins with an iron-porphyrin complex as prosthetic group. They catalyze the oxidation of
substrate by peroxides, frequently via free-radical intermediates. The catalytic cycle involves changes in the redox states
of the prosthetic group, that can be monitored by changes in the intense absorption spectra. During the past decades, considerable
scientific effort has been put into the elucidation of the mechanisms of reactions catalyzed by these enzymes. Radiation-chemical
techniques have made an important contribution by providing information on the redox states of the enzymes and their interconversions,
as well as on the properties of the free-radical intermediates involved. 相似文献
64.
Alberto Girlando Cristina Sissa Francesca Terenziani Anna Painelli Anna Chwialkowska Geoffrey J Ashwell 《Chemphyschem》2007,8(15):2195-2201
We report visible, Raman, and infrared spectra of self-assembled monolayers (SAMs) formed by the donor-(pi-bridge)-acceptor chromophore, Z-beta-[N-(omega-acetylthioalkyl)-4-quinolinium]-alpha-cyano-4-styryldicyanomethanide (CH3CO-S-CnH2n-Q3CNQ where n=8, 10), on gold-coated substrates. The data are compared with the spectra collected for the same compound in solution and in the solid state, and with those obtained for a Langmuir-Blodgett (LB) monolayer of C16H33-Q3CNQ deposited on gold. Spectral analysis confirms that in solution, in the solid state and in the LB film the chromophore has a zwitterionic (D+-pi-A-) ground state. At variance with this well-known result, our data show that in SAMs deposited on gold the chromophore has a more neutral, quinoid ground state. We relate this difference to the different packing of the molecules in the two different films: in SAMs in fact the chromophores stand almost vertical with respect to the substrate, whereas in LB films they make an angle of about 45 degrees. The Q3CNQ molecule is a well-known molecular rectifier, and for SAMs we were able to check the direction of electron flow at forward bias on the same samples that have been characterized spectroscopically, shedding light on the rectification mechanism. 相似文献
65.
Analysis of cyanobacterial toxins by hydrophilic interaction liquid chromatography-mass spectrometry 总被引:5,自引:0,他引:5
The combination of hydrophilic interaction liquid chromatography with electrospray mass spectrometry (HILIC-MS) has been investigated as a tool for the analysis of assorted toxins produced by cyanobacteria. Toxins examined included saxitoxin and its various analogues (1-18), anatoxin-a (ATX-a, 19), cylindrospermopsin (CYN, 20), deoxycylindrospermopsin (doCYN, 21), and microcystins-LR (22) and -RR (23). The saxitoxins could be unequivocally detected in one isocratic analysis using a TSK gel Amide-80 column eluted with 65% B, where eluent A is water and B is a 95% acetonitrile/water solution, both containing 2.0 mM ammonium formate and 3.6 mM formic acid. The analysis of ATX-a, CYN and doCYN required 75% B isocratic. Simultaneous determination of 1-21 was also possible by using gradient elution. HILIC proved to be suitable for the analysis of microcystins, but peak shape was not symmetric and it was concluded that these compounds are best analysed using existing reversed-phase methods. The HILIC-MS method was applied to the analysis of field and cultured samples of Anabaena circinalis and Cylindrospermopsis raciborskii. In general, the method proved quite robust with similar results obtained in two different laboratories using different instrumentation. 相似文献
66.
NiCl(2)(dppe)-catalyzed cross-coupling of aryl mesylates, arenesulfonates, and halides with arylboronic acids 总被引:2,自引:0,他引:2
An investigation of the NiCl(2)(dppe)-, NiCl(2)(dppb)-, NiCl(2)(dppf)-, NiCl(2)(PCy(3))(2)-, and NiCl(2)(PPh(3))(2)-catalyzed cross-coupling of the previously unreported aryl mesylates, and of aryl arenesulfonates, chlorides, bromides, and iodides containing electron-withdrawing and electron-donating substituents with aryl boronic acids, in the absence of a reducing agent, is reported. NiCl(2)(dppe) was the only catalyst that exhibited high and solvent-independent activity in the two solvents investigated, toluene and dioxane. NiCl(2)(dppe) with an excess of dppe, NiCl(2)(dppe)/dppe, was reactive in the cross-coupling of electron-poor aryl mesylates, tosylates, chlorides, bromides, and iodides. This catalyst was also efficient in the cross-coupling of aryl bromides and iodides containing electron-donating substituents. Most surprisingly, the replacement of the excess dppe from NiCl(2)(dppe)/dppe with excess PPh(3) generated NiCl(2)(dppe)/PPh(3), which was found to be reactive for the cross-coupling of both electron-rich and electron-poor aryl mesylates and chlorides. Therefore, the solvent-independent reactivity of NiCl(2)(dppe) provides an inexpensive and general nickel catalyst for the cross-coupling of aryl mesylates, tosylates, chlorides, bromides, and iodides with aryl boronic acids. 相似文献
67.
Miles S. CongreveCorinne Kay Jan J. ScicinskiSteven V. Ley Geoffrey WilliamsPeter J. Murray Stephen C. McKeownStephen P. Watson 《Tetrahedron letters》2003,44(21):4153-4156
The development of a versatile amine releasing linker based on the modified o-nitrobenzene sulfonamide protective group is described. This new N-Boc-o-nitrobenzenesulfonamide (Boc-ONBS) linker enables the elaboration on resin of primary and secondary amines by sequential substitution of the sulfonamide moiety using the Mitsunobu reaction. A 16-member array of secondary and Boc protected primary amines was then prepared using this linker. 相似文献
68.
Huang F Switek KA Zakharov LN Fronczek FR Slebodnick C Lam M Golen JA Bryant WS Mason PE Rheingold AL Ashraf-Khorassani M Gibson HW 《The Journal of organic chemistry》2005,70(8):3231-3241
Four new bis(m-phenylene)-32-crown-10-based cryptands with different third bridges were prepared. Their complexes with paraquat derivatives were studied by proton NMR spectroscopy, mass spectrometry, and X-ray analysis. It was found that these cryptands bind paraquat derivatives very strongly. Specifically, a diester cryptand with a pyridyl nitrogen atom located at a site occupied by either water or a PF(6) anion in analogous complexes exhibited the highest association constant K(a) = 5.0 x 10(6) M(-1) in acetone with paraquat, 9000 times greater than the crown ether system. X-ray structures of this and analogous complexes demonstrate that improved complexation with this host is a consequence of preorganization, adequate ring size for occupation by the guest, and the proper location of the pyridyl N-atom for binding to the beta-pyridinium hydrogens of the paraquat guests. This readily accessible cryptand is one of the most powerful hosts reported for paraquats. 相似文献
69.
Manfred Bortz Robert Bau Jörg J. Schneider Sax A. Mason 《Journal of Cluster Science》2001,12(1):285-291
The structure of H3Co2[C5H2(t-Bu)3]2 has been analyzed by low-temperature single-crystal neutron diffraction techniques, and shown to consist of two CoCp moieties with three hydride ligands bridging the central Co–Co bond. Despite a fairly extensive twinning problem, the structure could be solved and successfully refined to a final R factor of 9.2% for 2024 reflections. Average molecular parameters in the H3Co2 core of the molecule are as follows: Co–Co=2.275(21) Å, Co–H=1.637(16) Å, HH=2.050(20) Å, Co–H–Co=88.0(9)°, H–Co–H=77.0(7)°. Also included in this paper is a discussion on the molecular dimensions of symmetric hydride-bridged dinuclear systems (M(-H)nM, n=1, 2, 3, 4) that have been studied to date by neutron diffraction. 相似文献
70.
The intensities of the ΔM = ± 1 component of the 7fo→ 5D2 transition in D3 complexes containing the [ EuO9] cluster, and of other d-d or f-f transitions in D3 complexes with the yz- and xz-components of the electric quadrupole as the leading moment, are found to be dependent upon the polarizability anisotropy of the ligands. The expectation is supported by determinations of the single-crystal absorption intensities of Na3 [Eu(diglycollate)3]·2NaClO4·6H2O and [Eu(H2O)9] (C2H5SO4)3. 相似文献