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61.
Indranil Sinha Dr. Célia Fonseca Guerra Prof. Dr. Jens Müller 《Angewandte Chemie (International ed. in English)》2015,54(12):3603-3606
The first parallel‐stranded DNA duplex with Hoogsteen base pairing that readily incorporates an Ag+ ion into an internal mispair to form a metal‐mediated base pair has been created. Towards this end, the highly stabilizing 6 FP ‐Ag+‐ 6 FP base pair comprising the artificial nucleobase 6‐furylpurine ( 6 FP ) was devised. A combination of temperature‐dependent UV spectroscopy, CD spectroscopy, and DFT calculations was used to confirm the formation of this base pair. The nucleobase 6 FP is capable of forming metal‐mediated base pairs both by the Watson–Crick edge (i.e. in regular antiparallel‐stranded DNA) and by the Hoogsteen edge (i.e. in parallel‐stranded DNA), depending on the oligonucleotide sequence and the experimental conditions. The 6 FP ‐Ag+‐ 6 FP base pair within parallel‐stranded DNA is the most strongly stabilizing Ag+‐mediated base pair reported to date for any type of nucleic acid, with an increase in melting temperature of almost 15 °C upon the binding of one Ag+ ion. 相似文献
62.
Six‐Coordinate Group 13 Complexes: The Role of d Orbitals and Electron‐Rich Multi‐Center Bonding 下载免费PDF全文
Maarten G. Goesten Dr. Célia Fonseca Guerra Prof. Dr. Freek Kapteijn Prof. Dr. Jorge Gascon Prof. Dr. F. Matthias Bickelhaupt 《Angewandte Chemie (International ed. in English)》2015,54(41):12034-12038
Bonding in six‐coordinate complexes based on Group 13 elements (B, Al, Ga, In, Tl) is usually considered to be identical to that in transition‐metal analogues. We herein demonstrate through sophisticated electronic‐structure analyses that the bonding in these Group 13 element complexes is fundamentally different and better characterized as electron‐rich hypervalent bonding with essentially no role for the d orbitals. This characteristic is carried through to the molecular properties of the complex. 相似文献
63.
Ruiz JM Mulder RJ Fonseca Guerra C Bickelhaupt FM 《Journal of computational chemistry》2011,32(4):681-688
We have carried out an extensive exploration of gas‐phase alkyl cation affinities (ACA) of archetypal anionic and neutral bases across the periodic system using zeroth order regular approximation‐relativistic density functional theory at BP86/QZ4P//BP86/TZ2P. ACA values were computed for the methyl, ethyl, i‐propyl and t‐butyl cations and compared with the corresponding proton affinities (PA). One purpose of this work is to provide an intrinsically consistent set of values of the 298 K ACA of all anionic (XH) and neutral bases (XHn) constituted by maingroup‐element hydrides of groups 14–17 and the noble gases (group 18) along the periods 1–6. Another purpose is to determine and rationalize the trend in affinity for a cation as the latter varies from proton to t‐butyl cation. This undertaking is supported by quantitative bond energy decomposition analyses. Correlations are established between PA and ACA values. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2011 相似文献
64.
In this contribution, a pulse sequence is described for recording accordion-optimized DEPT experiments. The proposed ACCORDEPT experiment detects a wide range of one-bond coupling constants using accordion optimization. As a proof of concept, this strategy has been applied to a mesogen containing a large range of one-bond (1)J(CH) coupling constants associated with the various structural elements. The ACCORDEPT experiment afforded significant enhancements for the resonances with the larger (1)J(CH) couplings, similar SNR for aliphatic resonances, but reduced SNR for aliphatic resonances as compared with the standard DEPT experiment. In addition, the ACCORDEPT is straightforward to implement, does not require any supplementary calibration procedures and can be used under automated conditions without difficulty by inexperienced users. 相似文献
65.
Rendiconti del Circolo Matematico di Palermo Series 1 - 相似文献
66.
67.
Misbahul Ain Khan Alina Guerra Cosenza Gwynn Pennant Ellis 《Journal of heterocyclic chemistry》1982,19(5):1077-1085
Various 1H,6H-pyrano[2,3-c]pyrazol-6-ones (III-XXIII) were obtained from β-keto esters and 1H-pyrazol-5-ones or hydrazines. Nitrations, chlorinations and brominations of these pyranopyrazoles were also carried out giving the corresponding derivatives (XXIV-LXIV). The pyrone ring is the more reactive one in these reactions and the preferred position of attack is the 5-position. The substitution products are formed by the addition-elimination route. 相似文献
68.
Araújo MJ Mattar NS Reis AS Serra IC Fialho EM Assunção AK Dutra RP Nogueira AM Libério SA Guerra RN Lopes AS Ribeiro MN Nascimento FR 《Natural product research》2011,25(11):1037-1046
The propolis of Scaptotrigona aff. postica is popularly used in Maranh?o State, Brazil, for treating wounds and respiratory illnesses. Nevertheless, little is known about the chemical composition of this propolis and the adverse effects of its use. Hence, this study is a pharmacognostic characterisation of the propolis hydroalcoholic extract (PHE) from S. aff. postica. The methodology consisted of an evaluation of the sensory and chemical parameters. Chemical analysis of PHE indicated high concentrations of phenolic and triterpens substances, and the absence of steroids. Additionally, we evaluated the acute toxicity of propolis using 48 Swiss male and female mice. The animals received single doses of PHE (1000, 2000 or 4000 mg kg?1) orally and were observed for 14 days. After this period, the mice were sacrificed and the blood was used for biochemical and haematological evaluation. PHE did not induce any death, and the acute treatment significantly reduced serum concentrations of alanine aminotransferase and alkaline phosphatase. The resultant data indicate that PHE from S. aff. postica has low toxicity when used orally, even in high doses. 相似文献
69.
Francisco Gmez Robert Quintana Antxon Martez De Ilarduya Elisabet Rud Sebastin Muoz‐Guerra 《Journal of polymer science. Part A, Polymer chemistry》2005,43(1):92-100
A series of poly(butylene terephthalate) copolyesters containing 5‐tert‐butyl isophthalate units up to 50 mol %, as well as the homopolyester entirely made of these units, were prepared by polycondensation from a melt. The microstructure of the copolymers was determined by NMR to be random for the whole range of compositions. The effect exerted by the 5‐tert‐butyl isophthalate units on thermal, tensile, and gas transport properties was evaluated. Both the melting temperature (Tm) and crystallinity were found to decrease steadily with copolymerization, whereas the glass‐transition temperature (Tg) increased and the polyesters became more brittle. Permeability and solubility slightly increased with the content in substituted isophthalic units, whereas the diffusion coefficient remained practically constant. For the homopolyester poly(5‐tert‐butyl isophthalate), all these properties were found to deviate significantly from the general trend displayed by copolyesters, suggesting that a different structure in the solid state is likely adopted in this case. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 92–100, 2005 相似文献
70.
Francisca Zamora Khalid Hakkou Abdelilah Alla Manuel Rivas Isaac Roff Manuel Mancera Sebastin Muoz‐Guerra Juan A. Galbis 《Journal of polymer science. Part A, Polymer chemistry》2005,43(19):4570-4577
The synthesis and characterization of a new series of aromatic polyesters based on D‐mannitol and galactitol are described. These polyesters were obtained by polycondensation reaction of the terephthaloyl chloride or isophthaloyl chloride and 2,3,4,5‐tetra‐O‐methyl‐D‐mannitol or 2,3,4,5‐tetra‐O‐methyl‐galactitol in o‐dichlorobenzene. All the new polyesters were characterized by elemental analyses, GPC, IR, and NMR. They were soluble in chloroform, but insoluble in water and other polar oxygenated solvents. They showed a notable hygroscopicity, lower for those containing isophthalic units. DSC and X‐ray diffraction studies showed that D‐mannitol‐based polyesters were stiffer and less crystalline than those derived from galactitol, which presented a noticeably lower thermal stability. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4570–4577, 2005 相似文献