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101.
Gerrit E.W. Bauer Allan H. MacDonald Sadamichi Maekawa 《Solid State Communications》2010,150(11-12):459-460
102.
103.
Bond-switching rearrangement via hypervalent sulfur occurs during the reactions of 5-anilino-2-benzyl-3-oxo-Δ4–1,2,4-thiadiazoline 5 with electrophilic nitriles, isothiocyanates, carbon disulfide and ketenes, yielding the products 6 and 7. In contrast, N,N'-ditolylcarbodiimide reacts with 5 to give the normal addition product 8 , which rearranges only partially to 9 in several solvents (chloroform, acetonitrile and dimethyl sulfoxide). The equilibrium position depends on the temperature, favoring 9 at higher temperatures. 相似文献
104.
We demonstrate the influence of molecular weight and molecular weight asymmetry across an interface on the transient behavior of the interfacial tension. The interfacial tension was measured as a function of time for a range of polymer combinations with a broad range of interfacial properties using a pendant/sessile drop apparatus. The results show that neglecting mutual solubility, assumed to be a reasonable approximation in many cases, very often does not sustain. Instead, a diffuse interface layer develops in time with a corresponding transient interfacial tension. Depending on the specific combination of polymers, the transient interfacial tension is found to increase or decrease with time. The results are interpreted in terms of a recently proposed model [Shi et al., Macromolecules 37, 1591 (2004)], giving relative characteristic diffusion time scales in terms of molecular weight, molecular weight distribution, and viscosities. However, the time scales obtained from this theoretical approach do not give a conclusive trend. Using oscillatory dilatational interfacial experiments the viscoelastic behavior of these diffusive interfaces is demonstrated. The time evolution of the interfacial tension and the dilatational elasticity show the same trend as predicted by the theory of diffuse interfaces, supporting the idea that the polymer combinations under consideration indeed form diffuse interfaces. The dilatational elasticity and the dilatational viscosity show a frequency dependency that is described qualitatively by a simple Fickian diffusion model and quantitatively by a Maxwell model. The characteristic diffusion times provided by the latter show that the systems with thick interfaces (tens of microseconds and more) can be considered as slower diffusive systems compared to the systems with thinner interfaces (a few micrometers in thickness and less) can be considered as fast diffusive systems. 相似文献
105.
Gerrit L'Abb Ernestine Albrecht Suzanne Toppet 《Journal of heterocyclic chemistry》1991,28(6):1619-1623
5-Amino-3-oxo-Δ4-1,2,4-thiadiazolines 5a,b react with isocyanates to yield 1,2,4-thiadiazolidine derivatives 9a-d via bond switching of the corresponding isomers 7 . The same type of products 9e-m was obtained by treatment of 5-amino-1,2,3,4-thiatriazoles 6a-d with two equivalents of isocyanate. 相似文献
106.
Zschörnig O Paasche G Thieme C Korb N Arnold K 《Colloids and surfaces. B, Biointerfaces》2005,42(1):69-78
Lysozyme is a globular protein which is known to bind to negatively charged phospholipid vesicles. In order to study the relationship between charge state of the protein and its interaction with negatively charged phospholipid membranes chemical modifications of the proteins were carried out. Succinylation and carbodiimide modification was used to shift the isoelectric point of lysozyme to lower and higher pH values, respectively. The binding of the modified lysozyme to phospholipid vesicles prepared from phosphatidic acid (PA) was determined using microelectrophoresis and ultracentrifugation. At acidic pH of the solution all lysozyme species reduced the surface charges of PA vesicles. Succinylated lysozyme (succ lysozyme) reduced the electrophoretic mobility (EPM) to nearly zero, whereas native lysozyme and carboxylated lysozyme (carbo lysozyme) changed the surface charge to positive values. At neutral pH, the reduction of surface charges was less for carbo lysozyme and unmodified lysozyme. Succ lysozyme did not change the EPM. Unmodified and carbo lysozyme decreased the magnitude of EPM, but the whole complex was still negatively charged. The bound fraction of all modified lysozyme to PA vesicles at high lysozyme/PA ratios was nearly constant at acidic pH. At low lysozyme/PA ratios the extent of bound lysozyme is changed in the order carbo>unmodified>succ lysozyme. Increasing the pH, the extent of bound lysozyme to PA large unilamellar vesicles (LUV) is reduced, at pH 9.0 only 35% of carbo lysozyme, 23% of unmodified lysozyme is bound, whereas succ lysozyme does not bind at pH 7.4 and 9.0. At low pH, addition of all lysozyme species resulted in a massive aggregation of PA liposomes, at neutral pH aggregation occurs at much higher lysozyme/PA ratios. Lysozyme binding to PA vesicles is accompanied by the penetration of lysozyme into the phospholipid membrane as measured by monolayer techniques. The penetration of lysozyme into the monolayer was modulated by pH and ionic strengths. The interaction of lysozyme with negatively charged vesicles leads to a decrease of the phospholipid vesicle surface hydration as measured by the shift of the maximum of the fluorescence signal of a headgroup labeled phospholipid. The binding of bis-ANS as an additional indicator for the change of surface hydrophobicity is increased at low pH after addition of lysozyme to the vesicles. More hydrophobic patches of the lysozyme-PA complex are exposed at low pH. At low pH the binding process of lysozyme to PA vesicles is followed by an extensive intermixing of phospholipids between the aggregated vesicles, accompanied by a massive leakage of the vesicle aqueous content. The extent of lysozyme interaction with PA LUV at neutral and acidic pH is in the order carbo lysozyme>lysozyme>succ lysozyme. 相似文献
107.
Schüürmann G Funar-Timofei S 《Journal of chemical information and computer sciences》2003,43(5):1502-1512
For a data set with 30 direct azo dyes taken from literature, quantitative structure-activity relationship (QSAR) analyses have been performed to model the affinity of the dye molecules for the cellulose fiber. The electronic structure of the compounds was characterized using quantum chemical gas-phase (AM1) and continuum-solvation molecular orbital parameters. As regards the solution phase, COSMO appears to be better suited than SM2 in quantifying relative trends of the aqueous solvation energy. For the dye-fiber affinity, the leave-one-out prediction capability of multilinear regression equations is superior to CoMFA, with predictive squared correlation coefficients ranging from 0.63 (pure CoMFA) to 0.89. At the same time, solution-phase CoMFA is superior to previously derived AM1-based CoMFA models. As a general trend, the dye-fiber affinity increases with increasing electron donor capacity that corresponds to an increasing hydrogen bond acceptor strength of the azo dyes. The discussion includes the consideration of structural features that are likely to be involved in dye-fiber and dye-dye hydrogen bonding interactions, and possible links between CoMFA electrostatic results and the atomic charge distribution of the compounds. 相似文献
108.
Linnea Lindh Olga Gordivska Samuel Persson Hannes Michaels Hao Fan Pavel Chbera Nils W. Rosemann Arvind Kumar Gupta Iacopo Benesperi Jens Uhlig Om Prakash Esmaeil Sheibani Kasper S. Kjaer Gerrit Boschloo Arkady Yartsev Marina Freitag Reiner Lomoth Petter Persson Kenneth Wrnmark 《Chemical science》2021,12(48):16035
A new generation of octahedral iron(ii)–N-heterocyclic carbene (NHC) complexes, employing different tridentate C^N^C ligands, has been designed and synthesized as earth-abundant photosensitizers for dye sensitized solar cells (DSSCs) and related solar energy conversion applications. This work introduces a linearly aligned push–pull design principle that reaches from the ligand having nitrogen-based electron donors, over the Fe(ii) centre, to the ligand having an electron withdrawing carboxylic acid anchor group. A combination of spectroscopy, electrochemistry, and quantum chemical calculations demonstrate the improved molecular excited state properties in terms of a broader absorption spectrum compared to the reference complex, as well as directional charge-transfer displacement of the lowest excited state towards the semiconductor substrate in accordance with the push–pull design. Prototype DSSCs based on one of the new Fe NHC photosensitizers demonstrate a power conversion efficiency exceeding 1% already for a basic DSSC set-up using only the I−/I3− redox mediator and standard operating conditions, outcompeting the corresponding DSSC based on the homoleptic reference complex. Transient photovoltage measurements confirmed that adding the co-sensitizer chenodeoxycholic acid helped in improving the efficiency by increasing the electron lifetime in TiO2. Time-resolved spectroscopy revealed spectral signatures for successful ultrafast (<100 fs) interfacial electron injection from the heteroleptic dyes to TiO2. However, an ultrafast recombination process results in undesirable fast charge recombination from TiO2 back to the oxidized dye, leaving only 5–10% of the initially excited dyes available to contribute to a current in the DSSC. On slower timescales, time-resolved spectroscopy also found that the recombination dynamics (longer than 40 μs) were significantly slower than the regeneration of the oxidized dye by the redox mediator (6–8 μs). Therefore it is the ultrafast recombination down to fs-timescales, between the oxidized dye and the injected electron, that remains as one of the main bottlenecks to be targeted for achieving further improved solar energy conversion efficiencies in future work.Iron-based photosensitizers for dye-sensitized solar cells with a rod-like push–pull design. Solar cell performance was limited by ultrafast (sub-ps) recombination, but yielded better performance than the homoleptic parent photosensitizer. 相似文献
109.
110.
Willie J.G.M. Peunenburg Guido J.M. Dormans Gerrit J. Bezemer Henk M. Buck 《Tetrahedron》1984,40(23):4959-4962
On the basis of the known preferential conformations of 8-oxo-germacrene B 7 it was possible to predict the resulting configurations at the chiral centres upon LiAlH4,-reduction and cyclopropanation. Further analysis of 8-hydroxy-germacrene B,1 and the cyclopropane derivatives of 7,8 and 9 afforded the prediction that the ultimate product distribution of the 4,5- and 1, 10-cyclopropane derivatives of 1 (i.e. 2-5) will be essentially independent of the reaction sequence. The prediction was vindicated by the observation of stereo- and regio-selective formation of 2-5, on reaction of 7 with the Simmons-Smith reagent and LiAlH4. Assignment of the relative configurations at the three chiral centres in each of the products 2-5 could be achieved by combining the two reaction routes. This assignment was based on an earlier performed conformational analysis of 1. 相似文献