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121.
The synthesis and crystal structures of five new analogues of the supramolecular copper(II) organophosphonate [CuII(phen)2Cl][(C6H5PO(OH)2)((OH)O2PC6H5)] (1) are presented. The structures contain substituted phenylphosphonic acids, and are of the general formula [CuII(phen)2Cl][(XPO(OH)2)((OH)O2PX)] · Z, where X = o-CH3(C6H5) (2); X = p-CH3(C6H5), Z = H2O · 2CH3CH2OH (4); X = o-NO2(C6H5), m-NO2(C6H5) (5); X = m-NO2(C6H5) (6); X = C10H7 (7). 相似文献
122.
Three di-Schiff-base ligands, N,N′-bis(salicylidene)-1,3-propanediamine (H2Salpn), N,N′-bis(salicylidene)-1,3-pentanediamine (H2Salpen) and N,N′-bis(salicylidine)-ethylenediamine (H2Salen) react with Ni(SCN)2 · 4H2O in 2:3 molar ratios to form the complexes; mononuclear [Ni(HSalpn)(NCS)(H2O)] · H2O (1a), trinuclear [{Ni(Salpen)}2Ni(NCS)2] (2b) and trinuclear [{Ni(Salen)}2Ni(NCS)2] (3) respectively. All the complexes have been characterized by elemental analyses, IR and UV–VIS spectra, and room temperature magnetic susceptibility measurements. The structures of 1a and 2b have been confirmed by X-ray single crystal analysis. In complex 1a, the Ni(II) atom is coordinated equatorially by the tetradentate, mononegative Schiff-base, HSalpn. Axial coordination of isothiocyanate group and a water molecule completes its octahedral geometry. The hydrogen atom attached to one of the oxygen atoms of the Schiff base is involved in a very strong hydrogen bond with a neighboring unit to form a centrosymmetric dimer. In 2b, two square planar [Ni(Salpen)] units act as bidentate oxygen donor ligands to a central Ni(II) which is also coordinated by two mutually cis N-bonded thiocyanate ligands to complete its distorted octahedral geometry. Complex 3 possesses a similar structure to that of 2b. A dehydrated form of 1a and a hydrated form of 2b have been obtained and characterized. The importance of electronic and steric factors in the variation of the structures is discussed. 相似文献
123.
Differential scanning calorimetry was used to investigate the confinement effects on the phase transition behaviour of a discotic liquid crystal. The liquid crystal studied is the hexa-n-octanoate of rufigallol (RHO); Millipore membranes of various pore sizes were the confining materials. The polymorphism of RHO is affected by confinement. The transition from an enantiotropic columnar phase (D1) to a monotropic columnar phase (D2) is supressed in membranes with pore sizes 500 A. The transformation from D1 to the crystalline phase is also perturbed, particularly in the membrane having an average pore size of 250 A. In the first case the crystal formed displays a double-melting endotherm, with a distinct structure melting at lower temperatures; in the other, the induction period of isothermal crystallization becomes longer and the global rate of crystallization is slowed. However, confinement shows no effect on the overall crystallization mechanism; a similar Avrami constant of n ~ 3 was obtained for both confined and bulk RHO. An analysis of the results is presented. 相似文献
124.
The thermal degradation of a series of polybenzoxazines based on bisphenol A and various aliphatic amines has been studied. Using the hyphenated techniques of thermogravimetric analysis-Fourier transform infrared spectroscopy (TGA-FTIR), and gas chromatography-mass spectrometry (GC-MS), the mechanisms of thermal decomposition have been proposed. It is also proposed that the Mannich base in polybenzoxazines plays a significant role in the thermal degradation of polybenzoxazines. The contribution of hydrogen bonding to the degradation mechanism of the Mannich base has been examined. The proposed mechanisms have also been supported through the thermal degradation study of benzoxazine model dimers. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1935–1946, 1998 相似文献
125.
Prof. Dr. Mario Waser Dr. Michael Winter M.Sc. Christopher Mairhofer 《Chemical record (New York, N.Y.)》2023,23(7):e202200198
(Thio)-urea-containing bifunctional quaternary ammonium salts emerged as powerful non-covalently interacting organocatalysts over the course of the last decade. The most commonly employed catalysts in this field are either based on Cinchona alkaloids, α-amino acids, or trans-cyclohexane-1,2-diamine. Our group has been heavily engaged in the design and use of such catalysts, i. e. trans-cyclohexane-1,2-diamine-based ones for around 10 years now, and it is therefore the intention of this short personal account to provide an overview of the, at least in our opinion, most significant and pioneering achievements in this field by looking on catalyst design and asymmetric method development, with a special focus on our own contributions. 相似文献
126.
Simisola Ajayi Iman Asakereh Hanieh Rezasoltani David Davidson Prof. Dr. Mazdak Khajehpour 《Chemphyschem》2023,24(7):e202200731
The transfer model suggests that urea unfolds proteins mainly by increasing the solubility of the amide backbone, probably through urea-induced increase in hydrogen bonding. Other studies suggest that urea addition increases the magnitude of solvent-solute van der Waals interactions, which increases the solubility of nonpolar sidechains. More recent analyses hypothesize that urea has a similar effect in increasing the solubility of backbone and sidechain groups. In this work, we compare the effects of urea addition on the solvation of amides and alkyl groups. At first, we study the effects of urea addition upon solvent hydrogen bonding acidity and basicity through the perturbation in the fluorescence spectrum of probes 1-AN and 1-DMAN. Our results demonstrate that the solvent's hydrogen bonding properties are minimally affected by urea addition. Subsequently, we show that urea addition does not perturb the intra-molecular hydrogen bonding in salicylic acid significantly. Finally, we investigate how urea preferentially interacts with amide and alkyl groups moieties in water by comparing the effects of urea addition upon the solubility of acetaminophen and 4-tertbutylphenol. We show that urea affects amide and t-butyl solubility (lowers the transfer free energy of both amide (backbone) and alkyl (sidechain) groups) in a similar fashion. In other words, preferential interaction of urea with both moieties contributes to protein denaturation. 相似文献