Dynamic Behavior of Poly(2-vinylpyridine) in Solution Studied by 13C Nuclear Magnetic Relaxation

Abstract: The dynamics of poly(2-vinylpyridine) in chloroform solution has been examined by C-13 spin-lattice relaxation time and NOE measurements as a function of temperature. The experiments were performed at 50.3 and 100.6 MHz. The backbone carbon relaxation data have been analyzed in terms of six motional models. Among these models, the models which consider conformational transitions and bond librations for the backbone were found to be more successful. Pyridyl ring motion has been modeled as a restricted rotation with the rotational amplitude varying with temperature. The activation energy parameters obtained from the relaxation data of the pyridyl ring carbon have been compared with the energy barrier for ring rotation estimated from conformational energy calculations using the AM1 semiempirical quantum chemical method. The results of the conformational energy calculations support the description of pyridyl ring motion as a restricted rotation.

1H and 13C NMR spectral studies of conformation of some N-(2-pyridinyl)-3-pyridinecarboxamides

The 1H and 13C NMR spectra of N-(2-pyridinyl)-, N-(4-methyl2-pyridinyl)-, and N-(6-methyl-2-pyridinyl)-3-pyridine-carboxamides (1�3, respectively) and 3-pyridinecarboxamide (4) in different solvents have been analysed using COSY, HETCOR, chemical shift and coupling constant correlations. The conformations of 1�4 have been obtained by utilizing the NMR spectra, NOE experiments and MINDO/3 calculations. In dilute solutions, the 2-pyridyl ring is coplanar with the amide group while the 3-pyridyl ring is apparently not. Compounds 1�3 dimerize through cooperative hydrogen bonding in concentrated CDCl3 solution (approximately 0.1 M) and the structure of the dimer resembles some of the DNA base-pairs. Hydrogen bonding between N---H and the solvent molecules hinders dimerization in (CD3)2CO and CD3CN.

13C-1H HSQC Experiment of Probe Molecules Aligned in Thermotropic Liquid Crystals: Sensitivity and Resolution Enhancement in the Indirect Dimension

The spectra of molecules oriented in liquid crystalline media are dominated by partially averaged dipolar couplings. In the 13C–1H HSQC, due to the inefficient hetero-nuclear dipolar decoupling in the indirect dimension, normally carried out by using a π pulse, there is a considerable loss of resolution. Furthermore, in such strongly orienting media the 1H–1H and 13C–1H dipolar couplings leads to fast dephasing of transverse magnetization causing inefficient polarization transfer and hence the loss of sensitivity in the indirect dimension. In this study we have carried out 13C–1H HSQC experiment with efficient polarization transfer from 1H to 13C for molecules aligned in liquid crystalline media. The homonuclear dipolar decoupling using FFLG during the INEPT transfer delays and also during evolution period combined with the π pulse heteronuclear decoupling in the t1 period has been applied. The studies showed a significant reduction in partially averaged dipolar couplings and thereby enhancement in the resolution and sensitivity in the indirect dimension. This has been demonstrated on pyridazine and pyrimidine oriented in the liquid crystal. The two closely resonating carbons in pyrimidine are better resolved in the present study compared to the earlier work [H.S. Vinay Deepak, Anu Joy, N. Suryaprakash, Determination of natural abundance 15N–1H and 13C–1H dipolar couplings of molecules in a strongly orienting media using two-dimensional inverse experiments, Magn. Reson. Chem. 44 (2006) 553–565].

Si nanowire growth on sapphire: Classical incubation, reverse reaction, and steady state supersaturation

Si nanowire growth on sapphire substrates by the vapor-liquid-solid (VLS) method using Au catalyst particles has been studied. Sapphire was chosen as the substrate to ensure that the vapor phase is the only source of Si. Three hitherto unreported observations are described. First, an incubation period of 120-480 s, which is shown to be the incubation period as defined in classical nucleation theory, is reported. This incubation period permits the determination of a desolvation energy of Si from Au-Si alloys of 15 kT. Two, transmission electron microscopy studies of incubation, point to Si loss by reverse reaction as an important part of the mechanism of Si nanowire growth by VLS. Three, calculations using these physico-chemical parameters determined from incubation and measured steady state growth rates of Si nanowires show that wire growth happens from a supersaturated catalyst droplet. (C) 2015 AIP Publishing LLC.

Survival and Growth of American Alligator (Alligator mississippiensis) hatchlings after artificial incubation and repatriation

Hatchling American Alligators (Alligator mississippiensis) produced from artificially incubated wild eggs were returned to their natal areas (repatriated). We compared artificially incubated and repatriated hatchlings released within and outside the maternal alligator’s home range with naturally incubated hatchlings captured and released within the maternal alligator’s home range on Lake Apopka, Lake Griffin, and Orange Lake in Florida. We used probability of recapture and total length at approximately nine months after hatching as indices of survival and growth rates. Artificially incubated hatchlings released outside of the maternal alligator’s home range had lower recapture probabilities than either naturally incubated hatchlings or artificially incubated hatchlings released near the original nest site. Recapture probabilities of other treatments did not differ significantly. Artificially incubated hatchlings were approximately 6% shorter than naturally incubated hatchlings at approximately nine months after hatching. We concluded that repatriation of hatchlings probably would not have long-term effects on populations because of the resiliency of alligator populations to alterations of early age-class survival and growth rates of the magnitude that we observed. Repatriation of hatchlings may be an economical alternative to repatriation of older juveniles for population restoration. However, the location of release may affect subsequent survival and growth.

Academic spin-offs incubation strategies: the case of the Andalusian region

[EN] The objective of this paper is to analyze the incubation strategies developed in the universities of Andalusia, a relatively low-income region of Spain, to promote the creation of university spin-offs. These strategies are also compared to the incubation models noted in the literature. The performance of the university spin-offs created and its relation to the incubation strategies developed by the university are also analysed. The analysis is based on data from a survey of nine public universities that carry out strategies for the promotion of university spin-offs. The result of the analysis shows that university spin-off incubation strategies in Andalusia present specific characteristics not covered by certain models that are well-known in the literature on innovation. Then, a new stage in the process of the university spin-off incubation is proposed. We consider it to be a pre-strategic stage to the academic spin-off incubation strategies. The analysis also finds certain environmental factors associated to those spin-offs promoted by Andalusian universities that achieve the highest level of performance. This result suggests that previous to making any decision involving investment into developing incubation strategies, universities should gauge whether they have sufficient resources and the possibilities of connecting with a Technology Park.