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181.
Facially coordinating triamine ligands with a cyclic backbone: some structure-stability correlations
Neis C Petry D Demangeon A Morgenstern B Kuppert D Huppert J Stucky S Hegetschweiler K 《Inorganic chemistry》2010,49(21):10092-10107
Metal complex formation of the two cyclic triamines 6-methyl-1,4-diazepan-6-amine (MeL(a)) and all-cis-2,4,6-trimethylcyclohexane-1,3,5-triamine (Me(3)tach) was studied. The structure of the free ligands (H(x)MeL(a))(x+) and H(x)Me(3)tach(x+) (0 ≤ x ≤ 3) was investigated by pH-dependent NMR spectroscopy and X-ray diffraction experiments. The crystal structure of (H(2)Me(3)tach)(p-O(3)S-C(6)H(4)-CH(3))(2) showed a chair conformation with axial nitrogen atoms for the doubly protonated species. In contrast to a previous report, Me(3)tach was found to be a stronger base than the parent cis-cyclohexane-1,3,5-triamine (tach); pK(a)-values of H(3)Me(3)tach(3+) (25 °C, 0.1 M KCl): 5.2, 7.4, 11.2. The crystal structures of (H(3)MeL(a))(BiCl(6))·2H(2)O and (H(3)MeL(a))(ClO(4))Cl(2) exhibited two distinct twisted chair conformations of the seven membered diazepane ring. [Co(MeL(a))(2)](3+) (cis: 1(3+), trans: 2(3+)), trans-[Fe(MeL(a))(2)](3+) (3(3+)), [(MeL(a))ClCd(μ(2)-Cl)](2) (4), trans-[Cu(MeL(a))(2)](2+) (5(2+)), and [Cu(HMeL(a))Br(3)] (6) were characterized by single crystal X-ray analysis of 1(ClO(4))(3)·H(2)O, 2Br(3)·H(2)O, 3(ClO(4))(3)·0.8MeCN·0.2MeOH, 4, 5Br(2)·0.5MeOH, and 6·H(2)O. Formation constants and redox potentials of MeL(a) complexes were determined by potentiometric, spectrophotometric, and cyclovoltammetric measurements. The stability of [M(II)(MeL(a))](2+)-complexes is low. In comparison to the parent 1,4-diazepan-6-amine (L(a)), it is only slightly enhanced. In analogy to L(a), MeL(a) exhibited a pronounced tendency for forming protonated species such as [M(II)(HMeL(a))](3+) or [M(II)(MeL(a))(HMeL(a))](3+) (see 6 as an example). In contrast to MeL(a), Me(3)tach forms [M(II)L](2+) complexes (M = Cu, Zn) of very high stability, and the coordination behavior corresponds mainly to an "all-or-nothing" process. Molecular mechanics calculations showed that the low stability of L(a) and MeL(a) complexes is mainly due to a large amount of torsional strain within the pure chair conformation of the diazepane ring, required for tridentate coordination. This behavior is quite contrary to Me(3)tach and tacn (tacn =1,4,7-triazacyclononane), where the main portion of strain is already preformed in the free ligand, and the amount, generated upon complex formation, is comparably low. 相似文献
182.
Alexandre M. Polozov 《Tetrahedron letters》2010,51(4):575-578
Isosteric replacement of the α,β-unsaturated amide at the C-7 position of indoles with a diverse set of five-membered amino-heterocycles including isoxazole, oxadiazole, thiadiazole and pyrazole followed by subsequent derivatization of the heterocyclic amino group to yield amides, sulfonamides and phosphoramides is described. Distinctive features of these procedures include the versatility and robust nature of the synthetic steps along with the high yields of the targeted molecules. 相似文献
183.
Alexandre A. Mikhailine 《Journal of organometallic chemistry》2010,695(14):1824-4431
Various cyclic phosphonium structures are formed in high yield by the deprotection of unstable phosphine-aldehydes in acidic solution. When there is a methylene spacer between the phosphine and the aldehyde, a phosphonium ion [PHR2CH2CH(OEt)2]Br2, R=iPrOH, Et is obtained. Reaction of these phosphonium salts with water produces the dimers [-PR2CH2CH(OH)-]2[Br]2 R = iPr, Et. When there is an ethylene spacer as in PPh2CH2CH2CH(OCH2CH2O), a remarkable tetramer with a 16-membered ring [-PPh2CH2CH2CH (OH)-]4[Cl]4 forms as one diastereomer in hydrochloric acid solution. Reaction of HCl with the protected phosphine-aldehyde with a propylene spacer (PPh2CH2CH2CH2CH(OCH2CH2O)) results in the formation of the monomeric phosphonium salt [-PPh2 CH2CH2CH2CH(OH)-]Cl with a 5-membered ring. Solid state structures of different ring types were determined using X-ray diffraction experiment. 相似文献
184.
185.
Chunyan Yang Xiaokun Hu Alexandre V. Loboda Robert H. Lipson 《Journal of the American Society for Mass Spectrometry》2010,21(2):294-299
In this work, a new absorbing candidate, rhodamine (R) 575, is described, which forms the basis of a binary matrix operating
at 532 nm. Analyte ionization is found to be much more efficient when the dye is combined with a proton donor such as hydrochloric
acid or α-cyano-4-hydroxycinnamic acid, or a proton acceptor such as sodium hydroxide. This makes the matrix more generic
than many others that have been tried. Furthermore, under visible illumination R575 produces very few chemical fragments,
making it useful for small molecular weight analyte detection. Spectra for a variety of analytes are shown. Insight into the
MALDI mechanism was obtained by comparing the similarities and differences of visible-MALDI with the more common UV and IR-MALDI
strategies. 相似文献
186.
Allegrand J Touboul D Schmitz-Afonso I Guérineau V Giuliani A Le Ven J Champy P Laprévote O 《Rapid communications in mass spectrometry : RCM》2010,24(24):3602-3608
Collision‐induced dissociation experiments of seven annonaceous acetogenins were carried out under high and low collision energy conditions. Each compound was studied as protonated or deprotonated and lithium‐ or sodium‐ cationized molecules, using ElectroSpray Ionisation (ESI) with a hybrid linear trap/orbitrap mass spectrometer (LTQ‐Orbitrap®). The same ion species were studied with a Matrix‐Assisted Laser Desorption Ionisation (MALDI) tandem mass spectrometer in a high collision energy regime (1 or 2 keV). Although each of the techniques showed some limitations in the detection of functional groups, unambiguous structural identification of the acetogenins was obtained. MALDI ToF‐ToF has the advantage over ESI‐based methods to provide mass spectra rich in informative fragments which allows the confirmation of some functional groups position. By contrast, ESI‐LTQ‐Orbitrap® analysis has the advantage over MALDI that the mass spectra are relatively simple with only fragments close to the functional groups. However, this technique needs to carry out experiments both in negative and positive ionization modes. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
187.
Jacson W. Menezes Jacqueline Ferreira Marcos J. L. Santos Lucila Cescato Alexandre G. Brolo 《Advanced functional materials》2010,20(22):3918-3924
Plasmonics is a fast developing research area with a great potential for practical applications. However, the implementation of plasmonic devices requires low cost methodologies for the fabrication of organized metallic nanostructures that covers a relative large area (~1 cm2). Here the patterning of periodic arrays of nanoholes (PANHs) in gold films by using a combination of interference lithography, metal deposition, and lift off is reported. The setup allows the fabrication of periodic nanostructures with hole diameters ranging from 110 to 1000 nm, for 450 and 1800 nm of periodicity, respectively. The large areas plasmonic substrates consist of 2 cm × 2 cm gold films homogeneously covered by nanoholes and gold films patterned with a regular microarray of 200 μm diameter circular patches of PANHs. The microarray format is used for surface plasmon resonance (SPR) imaging and its potential for applications in multiplex biosensing is demonstrated. The gold films homogeneously covered by nanoholes are useful as electrodes in a thin layer organic photovoltaic. This is first example of a large area plasmonic solar cell with organized nanostructures. The fabrication approach reported here is a good candidate for the industrial‐scale production of metallic substrates for plasmonic applications in photovoltaics and biosensing. 相似文献
188.
Waves scattered by a weakly inhomogeneous random medium contain a predominant single-scattering contribution as well as a multiple-scattering contribution which is usually neglected, especially for imaging purposes. A method based on random matrix theory is proposed to separate the single- and multiple-scattering contributions. The experimental setup uses an array of sources/receivers placed in front of the medium. The impulse responses between every couple of transducers are measured and form a matrix. Single-scattering contributions are shown to exhibit a deterministic coherence along the antidiagonals of the array response matrix, whatever the distribution of inhomogeneities. This property is taken advantage of to discriminate single- from multiple-scattered waves. This allows one to evaluate the absorption losses and the scattering losses separately, by comparing the multiple-scattering intensity with a radiative transfer model. Moreover, the relative contribution of multiple scattering in the backscattered wave can be estimated, which serves as a validity test for the Born approximation. Experimental results are presented with ultrasonic waves in the megahertz range, on a synthetic sample (agar-gelatine gel) as well as on breast tissues. Interestingly, the multiple-scattering contribution is found to be far from negligible in the breast around 4.3 MHz. 相似文献
189.
Loredo A Plessy A El Hafidi A Hamzaoui N 《The Journal of the Acoustical Society of America》2011,129(4):1905-1918
A numerical vibroacoustic model that can manage multilayered plates locally covered with damping patches is presented. All the layers can have an on-axis orthotropic viscoelastic behavior. Continuity of displacements and transverse shear stresses at each interface is enforced, which permits to write the entire displacement field in function of the displacements of the--common--first layer, leading to a two-dimensional plate model. The problem is then discretized by Rayleigh-Ritz's method using a trigonometric basis that includes both sine and cosine functions in order to treat various boundary conditions. The excitation can be of mechanical kind (concentrated or distributed forces) or of acoustic kind (plane wave of any incidence, diffuse field, etc.). The model permits to compute different vibroacoustic indicators: the mean square velocity of the plate, the radiation efficiency, and the transmission loss. Comparisons between the present model and numerical results from literature or finite element computations show that the model gives good results in both mechanical and acoustical aspects. Then, a comparison of the effects of different distributions of patches is presented. The role of the surface covering rate is first discussed, followed by a study involving different geometries for the same surface covering rate. 相似文献
190.
A theory is presented which allows us to accurately calculate the density profile of monovalent and multivalent counterions in suspensions of polarizable colloids or nanoparticles. In the case of monovalent ions, we derive a weak-coupling theory that explicitly accounts for the ion-image interaction, leading to a modified Poisson-Boltzmann equation. For suspensions with multivalent counterions, a strong-coupling theory is used to calculate the density profile near the colloidal surface and a Poisson-Boltzmann equation with a renormalized boundary condition to account for the counterion distribution in the far field. All the results are compared with the Monte?Carlo simulations, showing an excellent agreement between the theory and the simulations. 相似文献