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11.
Conformational characteristics of poly(vinylpyrrolidone). solvent-dependence of the chain dimensions
María Pilar Tarazona Enrique Saiz Ligia Gargallo Deodato Radic 《Macromolecular theory and simulations》1993,2(5):697-710
Conformational energies as function of rotational angles over two consecutive skeletal bonds for both meso and racemic diads of poly(Nvinyl-2-pyrrolidone) have been computed. The results of these calculations were used to formulate a statistical model that was then employed to calculate the unperturbed dimensions of this polymer. The conformational energies are sensitive to the Coulombic interactions, which are governed by the dielectric constant, of the solvent, and to the size of the solvent molecules. Consequently, the calculated values of the polymeric chain dimensions are strongly dependent on the nature of the solvent, as it was experimentally found before. 相似文献
12.
Reversible Activation of Water by an Air- and Moisture-Stable Frustrated Rhodium Nitrogen Lewis Pair
Dr. María Carmona Dr. Joaquina Ferrer Dr. Ricardo Rodríguez Dr. Vincenzo Passarelli Prof. Dr. Fernando J. Lahoz Dr. Pilar García-Orduña Dr. Laura Cañadillas-Delgado Prof. Dr. Daniel Carmona 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(60):13665-13670
[Cp*Rh(κ3N,N′,P- L )][SbF6] (Cp*=C5Me5), bearing a guanidine-derived phosphano ligand L , behaves as a “dormant” frustrated Lewis pair and activates H2 and H2O in a reversible manner. When D2O is employed, a facile H/D exchange at the Cp* ring takes place through sequential C(sp3)−H bond activation. 相似文献
13.
Lea Kremer Elisabeth Hennes Alexandra Brause Andrei Ursu Lucas Robke Hideaki T. Matsubayashi Yuta Nihongaki Jana Flegel Ivana Mejdrov Jan Eickhoff Matthias Baumann Radim Nencka Petra Janning Susanne Kordes Hans R. Schler Jared Sterneckert Takanari Inoue Slava Ziegler Herbert Waldmann 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(46):16770-16781
14.
González-Alvarez A Alfonso I Díaz P García-España E Gotor-Fernández V Gotor V 《The Journal of organic chemistry》2008,73(2):374-382
The interaction of a synthetic enantiopure azamacrocyclic receptor (L) with biologically important chiral dicarboxylates (A, 1-7) has been studied by means of potentiometric titrations in 0.15 M NaCl aqueous solution in a wide pH range. This macrocycle forms strong complexes of the type [HnLA](n-2) (with n = 0-5). As a general trend, the binding is much tighter at basic or neutral pH than in acidic medium. Interestingly, nonprotected excitatory amino acids (Asp and Glu) are strongly bound even at acidic pH. Regarding selectivity, the receptor showed stereoselective binding toward those substrates bearing an H-bonding donor at Calpha, being S-selective in most of the cases, except for glutamic acid. Thus, L displayed an excellent enantioselectivity for (S)-malate dianion (KS/KR = 11.50 at pH 10.0 and KS/KR = 6.86 at pH 7.0) and exhibited moderate enantiopreference for (S,S)-tartrate (KSS/KRR = 3.01 at pH 10 and KSS/KRR = 1.70 at pH 7.0). For this last anion, a very good diastereopreference was also observed (KSS/KRS = 8.46 at pH 10 and KSS/KRS = 4.99 at pH 7.0). On the contrary, L is smoothly R-selective toward (R)-Glu (KR/KS = 3.22 at pH 10 and KR/KS = 2.05 at pH 7.0) due to its longer and more flexible molecular structure. The stereoselectivity of the corresponding complexes decreased when decreasing pH values. For the hydroxy derivatives, mass spectrometry also reflected the trends observed by potentiometry and confirmed the receptor:dicarboxylate 1:1 stoichiometry of the supramolecular complexes. Additional experimental techniques were used to study the most stereoselective example. Solution studies by NMR suggested a good geometrical complementarity between the malate dianion and the receptor, which showed a predominant helical conformation in solution. Besides, self-diffusion rates (PGSE) of the diastereomeric complexes with malate also agree with binding data. Circular dichroism was also used in this case at different pH values, showing a very good correlation between the helical content of the receptor and the stereoselectivity of the molecular recognition process. 相似文献
15.
Rayón VM Redondo P Barrientos C Largo A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(26):6963-6975
First-row transition-metal dicarbides MC(2) (M=Sc-Zn) have been investigated by using quantum-mechanical techniques. The competition between cyclic and linear isomers in these systems has been studied and the bonding scheme for these compounds is discussed through topological analysis of electron density. All of the systems have been found to prefer a C(2v)-symmetric arrangement, although for ZnC(2) the energy difference between this and the linear isomer is rather small. In most cases the C(2v)-symmetric structure corresponds to a T-shaped structure, with the exceptions of TiC(2), CoC(2), and NiC(2) which have been shown to be true rings. A detailed analysis of the variation of the energy of the system with geometry has been carried out. An analysis of the bonding, taking into account the main interactions between the valence orbitals of both fragments, the M atom and the C(2) molecule, has allowed the main features of these compounds to be interpreted. A clear correlation between the dissociation energies of the first-row transition-metal dicarbides and the bonding energies of the corresponding met-cars was observed. 相似文献
16.
Rayón VM Redondo P Barrientos C Largo A 《The journal of physical chemistry. A》2007,111(28):6345-6353
A theoretical study of the first-row transition metal dicarbide cations MC2+ (M=Sc-Zn) has been carried out. Predictions for different molecular properties that could help in their eventual experimental detection have been made. Most MC2+ compounds prefer a C2v symmetric arrangement over the linear geometry. In particular, the C2v isomer is specially favored for early transition metals. Only for CuC2+ is the linear isomer predicted to be the global minimum, although by only 1 kcal/mol. In all cases the isomerization barrier between cyclic and linear species seems to be very small (below 2 kcal/mol). The topological analysis of the electronic density shows that most C2v isomers are T-shaped structures. In general, MC2+ compounds for early transition metals have larger dissociation energies than those formed by late transition metals. In most cases the dissociation energies for MC2+ compounds are much smaller than those obtained for their neutral analogues. An analysis of the bonding in MC2+ compounds in terms of the interactions between the valence orbitals of the fragments helps to interpret their main features. 相似文献
17.
Pastor-Belda Marta Arroyo-Manzanares Natalia Campillo Natalia Vias Pilar Guluarte Crystal Angulo Carlos Esteban Mara ngeles 《Chromatographia》2022,85(4):353-363
Chromatographia - Nucleobases, nucleosides and nucleotides can act as chemical markers and immunnostimulants. Ultra-high-performance liquid chromatography with electrospray ionization and... 相似文献
18.
Arajo Joana C. Teixeira Pilar Fangueiro Raul Ferreira Diana P. 《Cellulose (London, England)》2022,29(10):5659-5676
Cellulose - Core–shell nanoparticles (NPs) based on metal oxides, namely magnesium oxide (MgO) and silica (SiO2), are a fantastic alternative for natural fibers’ functionalization. In... 相似文献
19.
Summary Copper(II) and nickel(II) complexes with the Schiff base derived from 2-(2-aminophenyl)benzimidazole and salicylaldehyde, L, have been prepared. They are of the general types ML2X2 (M = Ni or Cu and X = Cl, Br, NO3 or ClO4) and NiL(NCS)2.The compounds have been characterized by elemental analyses, magnetic measurements, e.s.r., electronic and i.r. spectra studies. The i.r. spectra suggest that the molecule, and not the anion, of the Schiff base is coordinated as a bidentate ligand with the metal ion. Possible structures for the complexes have been proposed. 相似文献
20.
Complexes of TiCl4, VCl4 and SnX4 (X = Cl or Br) with Schiff bases derived from 2-aminobenzimidazole
Agueda Arquero Pilar Souza José A. García-Vázquez José R. Masaguer 《Transition Metal Chemistry》1985,10(11):424-426
Summary The reactions of anhydrous titanium(IV), tin(IV) and vanadium(IV) halides with Schiff bases derived from 2-aminobenzimidazole and 4-methylbenzaldehyde (abimbz) and salicylaldehyde (abisal), yield hexacoordinated complexes M(abimbz)Cl4 and M(abisal)2X4 (M = Ti, Sn or V; X = Cl or Br).The compounds have been characterized by elemental analyses, magnetic measurements, e.p.r., electronic and i.r. spectral studies. I.r. spectra suggest that the Schiff base (abimbz) is coordinated as a bidentate ligand with the metal ion and the (abisal) base acts as a monodentate ligand. 相似文献