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31.
Summary Two different types of porous glass (PG) were submitted to a thermal treatment in a temperature range from 620°C–700°C for 2 to 100 h. The materials thereby obtained have been characterized by static Secondary Ion Mass Spectrometry (SIMS). Special attention was paid to the change of the boron surface concentration. In addition we studied the specific surface area (SBET) dependence on the thermal treatment parameters, such as heating time and heating temperature. Selected PG materials have been modified with organosilanes and characterized prior to their use as packings in RP-HPLC.Dedicated to B. B.'s parents on their 60th birthday  相似文献   
32.
Artificial biomimetic chromophore-protein complexes inspired by natural visual pigments can feature color tunability across the full visible spectrum. However, control of excited state dynamics of the retinal chromophore, which is of paramount importance for technological applications, is lacking due to its complex and subtle photophysics/photochemistry. Here, ultrafast transient absorption spectroscopy and quantum mechanics/molecular mechanics simulations are combined for the study of highly tunable rhodopsin mimics, as compared to retinal chromophores in solution. Conical intersections and transient fluorescent intermediates are identified with atomistic resolution, providing unambiguous assignment of their ultrafast excited state absorption features. The results point out that the electrostatic environment of the chromophore, modified by protein point mutations, affects its excited state properties allowing control of its photophysics with same power of chemical modifications of the chromophore. The complex nature of such fine control is a fundamental knowledge for the design of bio-mimetic opto-electronic and photonic devices.  相似文献   
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34.
A new set of luminescent platinum(II) diimine complexes has been synthesized and characterized. The anionic ligands in these complexes are arylacetylides. The complexes are brightly emissive in fluid solution with relative emission quantum yields phiem ranging from 3 x 10(-3) to 10(-1). Two series of complexes have been investigated. The first has the formula Pt(Rphen)(C...CC6H5)2 where Rphen is 1,10-phenanthroline substituted in the 5-position with R = H, Me, Cl, Br, NO2, or C...CC6H5, while the second has the formula Pt(dbbpy)(C=CC6H4X)2 where dbbpy = 4,4'-di(tert-butyl)bipyridine and X = H, Me, F, or NO2. From NMR, IR, and electronic spectroscopies, all of the complexes are assigned a square planar coordination geometry with cis-alkynyl ligands. The crystal structure of Pt(phen)(Ce-CC6H4CH3)2 confirms this assignment. All of the complexes exhibit an absorption band at ca. 400 nm that corresponds to a Pt d-->pi*diimine charge-transfer transition. The variation of lambdamax for this band with substituent variation supports this assignment. From similar changes in the energy of the solution luminescence as a function of substituents R and X, the emissive excited state is also of MLCT origin, but with spin-forbidden character on the basis of excited-state lifetime measurements (0.01-5.6 micros). The complexes undergo electron-transfer quenching, showing good Stern-Volmer behavior using 10-methylphenothiazine and N,N,N',N'-tetramethylbenzidine as reductive quenchers. Excited-state reduction potentials are estimated on the basis of a simple thermochemical analysis. Crystal data for Pt(phen)(C...CC6H4CH3)2: monoclinic, space group C2/c, a = 19.0961(1) A, b = 10.4498(1) A, c = 11.8124(2) A, beta = 108.413(1) degrees, V = 2236.49 A3, number of reflections 1614, number of variables 150, R1 = 0.0163, wR2 (I > 2sigma) = 0.0410.  相似文献   
35.
Cs correctors have revolutionized transmission electron microscopy (TEM) in that they substantially improve point resolution and information limit. The object information is found sharply localized within 0.1 nm, and the intensity image can therefore be interpreted reliably on an atomic scale. However, for a conventional intensity image, the object exit wave can still not be detected completely in that the phase, and hence indispensable object information is missing. Therefore, for example, atomic electric-field distributions or magnetic domain structures cannot be accessed. Off-axis electron holography offers unique possibilities to recover completely the aberration-corrected object wave with uncorrected microscopes and hence we would not need a Cs-corrected microscope for improved lateral resolution. However, the performance of holography is affected by aberrations of the recording TEM in that the signal/noise properties ("phase detection limit") of the reconstructed wave are degraded. Therefore, we have realized off-axis electron holography with a Cs-corrected TEM. The phase detection limit improves by a factor of four. A further advantage is the possibility of fine-tuning the residual aberrations by a posteriori correction. Therefore, a combination of both methods, that is, Cs correction and off-axis electron holography, opens new perspectives for complete TEM analysis on an atomic scale.  相似文献   
36.
Summary.  Reactions of cyanomethanesulfonamides with aromatic aldehydes in the presence of AcOH and piperidine produced the addition products, the 1-cyano-2-arylethenesulfonamides, whereas reactions with benzonitrile yielded the 2-amino-1-cyano-2-phenylethenesulfonamides only when done in THF with BuLi. No addition products were isolated from the analogue reactions with 2-hydroxybenzaldehyde (salicylaldehyde). Instead, we obtained 2-imino-2H-chromene-3-sulfonamides with good to excellent yields. These 2H-chromene derivatives allowed a number of transformations, from which the reactions with orthoformates opened an approach to the hitherto unknown benzopyrano[3,2-e] [1,2,4]thiadiazine ring system.  相似文献   
37.
The structures of 4‐nitrobenzene‐1,2‐diamine [C6H7N3O2, (I)], 2‐amino‐5‐nitroanilinium chloride [C6H8N3O2+·Cl, (II)] and 2‐amino‐5‐nitroanilinium bromide monohydrate [C6H8N3O2+·Br·H2O, (III)] are reported and their hydrogen‐bonded structures described. The amine group para to the nitro group in (I) adopts an approximately planar geometry, whereas the meta amine group is decidedly pyramidal. In the hydrogen halide salts (II) and (III), the amine group meta to the nitro group is protonated. Compound (I) displays a pleated‐sheet hydrogen‐bonded two‐dimensional structure with R22(14) and R44(20) rings. The sheets are joined by additional hydrogen bonds, resulting in a three‐dimensional extended structure. Hydrohalide salt (II) has two formula units in the asymmetric unit that are related by a pseudo‐inversion center. The dominant hydrogen‐bonding interactions involve the chloride ion and result in R42(8) rings linked to form a ladder‐chain structure. The chains are joined by N—H...Cl and N—H...O hydrogen bonds to form sheets parallel to (010). In hydrated hydrohalide salt (III), bromide ions are hydrogen bonded to amine and ammonium groups to form R42(8) rings. The water behaves as a double donor/single acceptor and, along with the bromide anions, forms hydrogen bonds involving the nitro, amine, and ammonium groups. The result is sheets parallel to (001) composed of alternating R55(15) and R64(24) rings. Ammonium N—H...Br interactions join the sheets to form a three‐dimensional extended structure. Energy‐minimized structures obtained using DFT and MP2 calculations are consistent with the solid‐state structures. Consistent with (II) and (III), calculations show that protonation of the amine group meta to the nitro group results in a structure that is about 1.5 kJ mol−1 more stable than that obtained by protonation of the para‐amine group. DFT calculations on single molecules and hydrogen‐bonded pairs of molecules based on structural results obtained for (I) and for 3‐nitrobenzene‐1,2‐diamine, (IV) [Betz & Gerber (2011). Acta Cryst. E 67 , o1359] were used to estimate the strength of the N—H...O(nitro) interactions for three observed motifs. The hydrogen‐bonding interaction between the pairs of molecules examined was found to correspond to 20–30 kJ mol−1.  相似文献   
38.
The chiral ligand N-methylephedrine (NME) was found to catalyse the addition of dimethylzinc to benzaldehyde in an enantiodivergent way, with a monomeric and a homochiral dimeric complex both catalysing the reaction at a steady state and giving opposite product enantiomers. A change in the sign of the enantiomeric product was thus possible by simply varying the catalyst loading or the ligand ee, giving rise to an enantiodivergent non-linear effect. Simulations using a mathematical model confirmed the possibility of such behaviour and showed that this can lead to situations where a reaction gives racemic products, although the system is composed only of highly enantioselective individual catalysts. Furthermore, depending on the dimer''s degree of participation in the catalytic conversion, enantiodivergence may or may not be observed experimentally, which raises questions about the possibility of enantiodivergence in other monomer/dimer-catalysed systems. Simulations of the reaction kinetics showed that the observed kinetic constant kobs is highly dependent on user-controlled parameters, such as the catalyst concentration and the ligand ee, and may thus vary in a distinct way from one experimental setup to another. This unusual dependency of kobs allowed us to confirm that a previously observed U-shaped catalyst order vs. catalyst loading-plot is linked to the simultaneous catalytic activity of both monomeric and dimeric complexes.

An asymmetric reaction consisting of competing monomeric and dimeric catalysts may explain enantiodivergent non-linear effects.  相似文献   
39.
Summary. Cyanomethanesulfonyl chloride was reacted with amines yielding cyanomethanesulfonamides which could be transformed into alkoxymethylidene and aminomethylidene derivatives. The reaction of alkoxymethylidene derivatives with phenylhydrazine resulted in the formation of 5-aminopyrazol-4-sulfonamides, whereas from cyanomethanesulfonamides via the N-hydroxyamidine derivatives and their reaction with esters 1,2,4-oxadiazol-3-methanesulfonamides became accessible. Nitrosation of cyanomethanesulfonamides yielded 2-hydroxyimino derivatives which were then transformed into 2-hydroxyimino N-hydroxyamidine derivatives, and finally cyclized into 4-amino-1,2,5-oxadiazol-3-sulfonamides. On the other hand diazotation of cyanomethanesulfonamides gave the 2-arylhydrazono derivatives, which after transformation into N-hydroxyamidine derivatives gave by reaction with POCl3 5-amino-1,2,3-triazol-4-sulfonamides. Finally, the reaction between cyanomethanesulfonamides and formamidinium acetate opened an easy access to 4-aminopyrimidine-5-sulfonamides, which could be transformed by trialkyl orthoformiates into substituted pyrimidino[4,5-e][1,2,4]thiadiazine derivatives. All intermediates as well as transformation products of the heterocyclic systems were isolated and well characterized. Mechanisms were discussed, and the stereochemistry, when necessary and possible, was elucidated.  相似文献   
40.
Three peroxomanganese(III) complexes [Mn(III)(O(2))(mL(5)(2))](+), [Mn(III)(O(2))(imL(5)(2))](+), and [Mn(III)(O(2))(N4py)](+) supported by pentadentate ligands (mL(5)(2) = N-methyl-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine, imL(5)(2) = N-methyl-N,N',N'-tris((1-methyl-4-imidazolyl)methyl)ethane-1,2-diamine, and N4py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) were generated by treating Mn(II) precursors with H(2)O(2) or KO(2). Electronic absorption, magnetic circular dichroism (MCD), and variable-temperature, variable-field MCD data demonstrate that these complexes have very similar electronic transition energies and ground-state zero-field splitting parameters, indicative of nearly identical coordination geometries. Because of uncertainty in peroxo (side-on η(2) versus end-on η(1)) and ligand (pentadentate versus tetradentate) binding modes, density functional theory (DFT) computations were used to distinguish between three possible structures: pentadentate ligand binding with (i) a side-on peroxo and (ii) an end-on peroxo, and (iii) tetradentate ligand binding with a side-on peroxo. Regardless of the supporting ligand, isomers with a side-on peroxo and the supporting ligand bound in a tetradentate fashion were identified as most stable by >20 kcal/mol. Spectroscopic parameters computed by time-dependent (TD) DFT and multireference SORCI methods provided validation of these isomers on the basis of experimental data. Hexacoordination is thus strongly preferred for peroxomanganese(III) adducts, and dissociation of a pyridine (mL(5)(2) and N4py) or imidazole (imL(5)(2)) arm is thermodynamically favored. In contrast, DFT computations for models of [Fe(III)(O(2))(mL(5)(2))](+) demonstrate that pyridine dissociation is not favorable; instead a seven-coordinate ferric center is preferred. These different results are attributed to the electronic configurations of the metal centers (high spin d(5) and d(4) for Fe(III) and Mn(III), respectively), which results in population of a metal-peroxo σ-antibonding molecular orbital and, consequently, longer M-O(peroxo) bonds for peroxoiron(III) species.  相似文献   
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