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191.
Donzello MP Ercolani C Gaberkorn AA Kudrik EV Meneghetti M Marcolongo G Rizzoli C Stuzhin PA 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(17):4009-4024
Co-cyclization of 1,2,5-thiadiazole-3,4-dicarbonitrile and 3,6-diamyloxyphthalodinitrile in the presence of magnesium or lithium amylate in amyl alcohol leads to mixtures containing the Mg derivatives of the symmetrical species tetrakis(1,2,5-thiadiazolo)porphyrazine, (S(4))PzH(2), and tetrakis(1,4-diamyloxybenzo)porphyrazine, (A(4))PzH(2), and the low-symmetry macrocycles bearing peripheral 1,2,5-thiadiazole and 1,4-diamyloxybenzene rings in the ratio 1:3, 2:2 (cis and trans), and 3:1, that is, (SA(3))PzH(2), (S(2)A(2))PzH(2), (SASA)PzH(2), and (S(3)A)PzH(2), respectively. The basic Mg materials were converted to the corresponding free-base macrocycles by treatment with CF(3)COOH. The species were separated from the mixtures by chromatography, either as Mg complexes or demetalated materials. With results on (S(4))PzH(2) and (SA(3))PzH(2) in hand, including crystallographic work on the latter, a general chemical physical investigation has been carried out of all the symmetrical and unsymmetrical free-base macrocycles. The structures of the species (S(2)A(2))PzH(2) and (A(4))PzH(2). were elucidated by single-crystal X-ray crystallography. The effect of the progressive variation of the macrocyclic structure along the series, from the symmetrical (S(4))PzH(2) to its symmetrical partner (A(4))PzH(2) via the low-symmetry 3:1, 2:2 (cis and trans), and 1:3 macrocycles, was studied by IR, (1)H NMR, and UV/Vis linear and nonlinear (optical limiting) measurements. The results are interpreted on the basis of intra- and intermolecular interactions between the electron-deficient 1,2,5-thiadiazole and the electron-donating 1,4-diamyloxybenzene moieties. 相似文献
192.
Rizzi C Rossini K Bruson A Sandri M Dal Belin Peruffo A Carraro U 《Electrophoresis》2002,23(19):3266-3269
Due to its high sensitivity, silver staining is a widely popular method for the revelation of biopolymers separated by both native and denaturing electrophoresis. A step-by-step method for the destaining and restaining of overdeveloped/overloaded silver-stained bands is described that is applicable to both proteins and nucleic acids. The procedure significantly improves densitometric analysis of gels that have been silver stained with either commercial kits or solutions made in-house. The method permits reproducible densitometry of silver-stained gels and allows quantification of both main and minor components in complex mixture of molecules resolved on the same gel slab. All steps may be interrupted and are readily reversible, allowing for facile densitometric analyses and photographic recording under optimized conditions. Furthermore, common artifacts such as differential staining of the two gel surfaces, localized uneven yellow-ochre background, and the presence of fold marks and fingerprints can be easily removed. 相似文献
193.
Casarin M Corvaja C Di Nicola C Falcomer D Franco L Monari M Pandolfo L Pettinari C Piccinelli F Tagliatesta P 《Inorganic chemistry》2004,43(19):5865-5876
194.
195.
Ferruccio Minzoni Corrado Pelizzi Giovanni Prater 《Journal of organometallic chemistry》1982,231(1):C6-C8
The reactions of [Mo(N22(dppe)2], (dppe Ph2PCH2CH2PPh2) with RC6H4NCO (R H, p-CH3, p-Cl) in benzene under irradiation produces [Mo(RC6H4NCO)2(dppe)2] in good yields. Comparison of the infrared data for these complexes, with those previously reported for metal complexes of CO2-like molecules suggest a η2-C,O coordination to the metal. 相似文献
196.
Gunaratne TC Gusev AV Peng X Rosa A Ricciardi G Baerends EJ Rizzoli C Kenney ME Rodgers MA 《The journal of physical chemistry. A》2005,109(10):2078-2089
Reported herein is a combination of experimental and DFT/TDDFT theoretical investigations of the ground and excited states of 1,4,8,11,15,18,22,25-Octabutoxyphthalocyaninato-nickel(II), NiPc(BuO)(8), and the dynamics of its deactivation after excitation into the S(1)(pi,pi) state in toluene solution. According to X-ray crystallographic analysis NiPc(BuO)(8) has a highly saddled structure in the solid state. However, DFT studies suggest that in solution the complex is likely to flap from one D(2)(d)-saddled conformation to the opposite one through a D(4)(h)-planar structure. The spectral and kinetic changes for the complex in toluene are understood in terms of the 730 nm excitation light generating a primarily excited S(1) (pi,pi) state that transforms initially into a vibrationally hot (3)(d(z)2,d(x)2(-)(y)2) state. Cooling to the zeroth state is complete after ca. 8 ps. The cold (d,d) state converted to its daughter state, the (3)LMCT (pi,d(x)2(-)(y)2), which itself decays to the ground state with a lifetime of 640 ps. The proposed deactivation mechanism applies to the D(2)(d)-saddled and the D(4)(h)-planar structure as well. The results presented here for NiPc(BuO)(8) suggest that in nickel phthalocyanines the (1,3)LMCT (pi,d(x)2(-)(y)2) states may provide effective routes for radiationless deactivation of the (1,3)(pi,pi) states. 相似文献
197.
A one-pot procedure is described for the preparation of 1H-pyrazole-carboximidamides 2, 1H-benzotriazole-carboximidamides 3 and guanidinylation of amines with 3. The X-ray crystal structure of N,N-dimethyl-1H-benzotriazole-1-carboximidamide 3b, has been determined. 相似文献
198.
Corrado Sarzanini Giovanni Sacchero Maurizio Aceto Ornella Abollino Edoardo Mentasti 《Journal of chromatography. A》1993,640(1-2):179-185
The ion-interaction chromatographic behaviour of Plasmocorinth B (a disulphonated azo dye) and of its complexes formed with metal ions in oxidation states + 2 and + 3 (Cu2+ Ni2+, Al3+, CO3+, Fe3+, Ga3+) was investigated. The effect of cationic ion-pairing agents (tetramethyl-, benzyltrimethyl- and tetrabutylammonium) was also evaluated in the presence of alkali metal ions competitors (Li+ and Na+). The effects of organic modifier and of pH were also considered. The remarkably different behaviour of the ligand and the complexes suggests the formation of M(II)L− and M(III)L22−. The stoichiometry of complexes was confirmed by applying the electrostatic theory derived from Gouy-Chapman and a modified Langmuir adsorption isotherm to the experimental data. 相似文献
199.
Bauer EM Donzello MP Ercolani C Masetti E Panero S Ricciardi G Rosa A Chiesi-Villa A Rizzoli C 《Inorganic chemistry》2003,42(2):283-293
Recrystallization of the previously reported monosolvated bis(phthalocyaninato)niobium(IV), [Pc2Nb].CINP (CINP = 1-chloronaphthalene), has allowed isolation of a single crystal of a new solvated form, i.e. [Pc2Nb]. 3.5CINP, whose structure has been elucidated by X-ray work: space group P2(1)/n (No. 14); a = 16.765(3), b = 23.800(4), c = 19.421(4) A; alpha = gamma = 90 degrees, beta = 92.51(2) degrees; Z = 4. The sandwiched material is a "stapled" molecule, characterized by the presence of two intramolecular interligand C-C sigma bonds and highly strained phthalocyanine units, as formerly observed by crystallographic work for its Ti(IV) analogue, [Pc2Ti], and the +1 corresponding fragment, [Pc2Nb]+, present in the species [Pc2Nb](l3)(l2)0.5.3.5CINP. [Pc2Nb] appears to be reluctant to undergo further oxidation above the +1 oxidation state. Detailed theoretical studies by DFT and TDDFT methods have been developed on [Pc2Nb] and [Pc2Nb]+, also extended for comparison to the Ti(IV) complex [Pc2Ti], and an adequate picture of the ground-state electronic structure of these species has been achieved. Moreover, the excitation energies and oscillator strengths calculated for the closed-shell systems, [Pc2Ti] and [Pc2Nb]+, provide a satisfactory interpretation of their characteristic visible optical spectra and help to rationalize the similar features observed in the visible spectrum of the open-shell "stapled" complex, [Pc2Nb]. Thin solid films (100-250 nm) of [Pc2Nb] deposited on ITO (indium-doped tin oxide) show a reversible redox process in neutral or acidic aqueous electrolytes. The electrochemical and electrochromic properties of the sandwiched complex, combined with impedance and UV/visible spectral measurements, are presented and discussed. The achieved electrochemical information, while substantially in keeping with the observed chemical redox behavior and theoretical predictions, qualifies [Pc2Nb] as an "optically passive" electrode and a promising material for its use in electrochromic devices. 相似文献
200.
Francesco Dondi Yassin Du Ale Kahie Gaetano Lodi Maurizio Remelli Pierluigi Reschiglian Corrado Bighi 《Analytica chimica acta》1986
Optimization of the chromatographic separation of flavonoid compounds in camomile extracts by the simplex method and the Monte Carlo method is described. Evaluation fo the number of peaks at unit resolution (Rs = 1) is used as the criterion of separation quality. The Davis-Giddings theory is applied in calculating the number of components and the results are validated by numerical simulations. Peak-purity checks for three identified compounds in commercial sample extracts are reported. Capacity factor patterns for 18 flavonoid and phenolic compounds over an extended range of methanol/aqueous buffer (pH 2.8) mobile phases are described. 相似文献